Herbicidal aryloxyphenyltriazolinones and related compounds

ABSTRACT

Herbicidal aryloxyphenyltriazolinones compounds which are ring-substituted aryloxyphenyltriazolinones, such as compounds of the formula ##STR1## where Z is O, S, NH, or alkylamino; and where R 2  is, for instance, C 2  H 5  OCO--CH(CH 3 )--O-- or CH 3  SO 2  --NH--CO--CH(CH 3 )--O--.

This application is a continuation-in-part of application Ser. No. 449,091 filed Dec. 8, 1989 which is a continuation-in-part of application Ser. No. 161,348 filed Feb. 19, 1988 now abandoned which is a continuation-in-part of application Ser. No. 898,453 filed Aug. 20, 1986 now abandoned.

This invention relates to novel herbicides for weed control in agriculture, horticulture and other fields where it is desired to control unwanted plant growth, such as grassy or broadleaf plant species. The information also relates to intermediates for the production of such herbicides.

A particularly effective aspect of this invention relates to herbicidal compounds of the formula ##STR2## where Q--Ar-- is a substituted phenyl radical (e.g. of the formula ##STR3## in which the substituent Q is at the 5-position (meta to the nitrogen of said formula I); Q is ##STR4## Z may be O, S, NH or alkylamino (such as lower alkylamino, e.g. methylamino).

R⁴ may be H or CH₃ ; and R³ may be OH, O⁻ ak⁺, alkoxy (e.g. lower alkoxy such as methoxy or ethoxy), cycloalkyloxy, lower alkenyloxy or alkynyloxy (e.g. allyloxy or propargyloxy), --O[CHR⁸ (CH₂)_(p) O]_(r) R⁹, amino, arylamino (e.g. phenylamino), alkylamino (e.g. lower alkylamino such as methylamino or dimethylamino), alkenylamino (e.g. diallylamino), alkoxyamino (e.g. lower alkoxyamino such as methoxyamino) or alkyl-, haloalkyl- or a arylsulfonylamino of the formula --N(alkyl)SO₂ R⁵, --NHSO₂ R⁵ or --N(SO₂ R⁵)SO₂ R⁶.

R⁵ and R⁶ may be independently alkyl (e.g. lower alkyl such as methyl, ethyl or propyl), haloalkyl (e.g. halo lower alkyl such as trifluoromethyl) or aryl such as phenyl or substituted phenyl, (e.g. alkoxy-substituted and/or halo-substituted phenyl).

n may be 1 or 2, m may be zero or 1, p may be 0 to 5, and r may be 1 to 6, preferably 1 to 3.

ak⁺ is a salt forming group such as sodium, potassium or ammonium.

R⁸ is H or CH₃ ; and p is 0 to 5; with the identity of R⁸ and the value of p being independently variable within an R³ radical (e.g. R³ ═O[CH(R⁸ ═CH₃)(CH₂)_(p)═1 O] [CH(R⁸ ═H)(CH₂)_(p)═3 O]R⁹);

R⁹ is alkyl.

R' may be H, alkyl (e.g. lower alkyl such as methyl), halogen such as Cl, Br or F, haloalkyl (e.g. lower haloalkyl such as CF₃, CH₂ F or CHF₂), nitro, NH₂, lower alkoxy or alkylthio (e.g. OCH₃ or SCH₃) or cyano. There may be a plurality of R' substituents on the same benzene ring.

In Formula I above, Ar, R^(a) and R^(b) are so chosen that when Q is methoxy or propargyloxy (instead of Q having the formula given above) the compound is a herbicide. Compounds in which Q in Formula I is methoxy or propargyloxy are, for convenience, here designated as the Methoxy Analogs and the Propargyloxy Analogs of the claimed novel compounds. Such Methoxy Analogs and Propargyloxy Analogs are well known in the art. For instance, the Methoxy Analog of Compounds 1-7, 26-72 and 88-91 of this application (see Table I below) is the compound 1-(4-chloro-2-fluoro-5-methoxyphenyl)-3-methyl-4-difluoromethyl-Δ.sup.2 -1,2,4-triazolin -5-one of Example 1D of International Application WO 85/04307 published Oct. 10, 1985 (U.S. Pat. No. 4,818,276), and the Propargyloxy Analog of said numbered compounds 1-7, 26-72 and 88-91 is the compound of Example 2 of that same International Application, while the Methoxy and Propargyloxy Analogs of compounds 82 and 92 are described in U.S. Pat. No. 4,398,943.

The substituents R^(a) and R^(b) on the triazolinone ring may be any of those known in the art. For instance, each may, independently, be lower alkyl or lower haloalkyl (e.g. fluoroalkyl). Additionally R^(a) may be alkenyl or alkynyl; and R^(b) may be hydrogen, halogen, alkylsulfonyl, alkylthio, alkoxy, or haloalkylsulfonyl Some examples of R^(a) an R^(b) substituents are found in Table 1.

R^(a) is preferably lower haloalkyl such as a fluoroalkyl, e.g. CF₂ CHF₂, particularly CHF₂.

R^(b) is preferably lower alkyl, e.g. CH₃.

Preferably, "Ar" carries a substituent (i.e. other than H) at the 2-position or the 4-position of the phenyl radical, most preferably at both the 2- and 4-positions.

X may be H, halogen such as Cl, Br or F (preferably Cl or F), alkyl (e.g. lower alkyl such as methyl), haloalkyl (e.g. lower haloalkyl such as CF₃, CH₂ F or CHF₂) or nitro; and

Y may be H, halogen such as Cl, Br or F (preferably Cl), alkyl (e.g. lower alkyl such as methyl), alkoxy (e.g. lower alkoxy such as methoxy), alkylthio (e.g. lower alkylthio such as methylthio), haloalkyl (e.g. lower haloalkyl such as fluoroalkyl), nitro, cyano, alkylsulfonyl alkyl, -SOCF3 or halo lower alkoxy such as --OCHF₂. Presently preferred X, Y substituents are: 2-F, 4-Cl; 2-F, 4-Br; 2,4-Cl₂ ; 2-Br, 4-Cl; and 2-F, 4-CF₃, particularly 2-F, 4-Cl and 2,4-Cl₂.

A broader aspect of the invention relates to herbicidal compounds of the formula ##STR5## in which Q' (which generically includes Q) is: ##STR6## in which R² may be H, halogen (such as Cl, Br or F), hydroxy, alkylcarbonyloxy (such as lower alkylcarbonyloxy, e.g. acetoxy), alkenyloxy (such as lower alkenyloxy, e.g. allyloxy), alkynyloxy (such as lower alkynyloxy, e.g. propargyloxy), alkyl (such as lower alkyl, e.g. methyl), haloalkyl (such as halo lower alkyl, e.g. CF₃, CHF₂, C₂ F₅ or CH₂ F), alkoxy (such as lower alkoxy, e.g. methoxy), haloalkoxy (such as halo lower alkoxy, e.g. OCHF₂ and OCF₃), nitro, amino, cyano, alkylthio (such as lower alkylthio e.g. methylthio), --COOH, COOR⁷, --CONHSO₂ R⁵, --CONH₂, --CONHR⁵, --CONHOR⁷ (where R⁷ is lower alkyl such as methyl), --COOCH(R⁴)COR³, -NHSO₂ R⁷, --N(SO₂ R⁷)₂, --SCH(R⁴)COR³ or --NHCH(R⁴)COR³ or R³ [CO--CH(R⁴)--O]_(n) - or NCCH(R⁴)O--[COCH(R⁴)--O] m--, and M is CH or N. R₇ is lower alkyl.

Z, m, n, r, p, R', R³, R⁴, R⁵, R⁶, R⁸ and R⁹ (as well as Ar, R^(a), R^(b), X and Y) are as described earlier. Of particular interest are those compounds in which R³ is --O[CH₂ (CH₂)_(p) O]_(r) CH₃. Ar, R^(a) and R^(b) are so chosen that the Methoxy Analog or Propargyloxy Analog (in which Q' is methoxy or propargyloxy instead of the Q' described above) is a herbicide.

In this application it is preferable that any alkyl, alkenyl, or alkynyl moiety (e.g., the hydrocarbon chain of an alkyl, haloalkyl, alkoxy, or alkylthio substituent) have up to 6 carbon atoms, and any cycloalkyl have from 3 to 7 carbon atoms.

In the preferred compounds of this invention, R^(a) and R^(b) and Ar (or X and Y) are so chosen that the Methoxy Analog or the Propargyloxy Analog of such preferred compound has marked herbicidal properties, such Analog showing at least 50% kill of at least one of the following modes at the rate of 0.5 kg/ha, and more preferably showing such 50% kill when applied at the rate of 0.1 kg/ha:

Species: velvetleaf (Abutilon theophrasti), green foxtail (Setaria viridis); Modes: pre-emergent, post-emergent. Testing for such herbicidal activity may be carried out in the manner described below (under the heading "Herbicidal Activity").

Representative compounds of this invention (including certain intermediates) are listed in Tables 1, 1A, 1B and 1C.

The compounds of this invention may be prepared by the use of steps generally described in the literature or by methods analogous or similar thereto and within the skill of the art. In Examples 1-7 below, the starting material is the Hydroxy Analog of the compound (which Hydroxy Analog may be obtained by treatment of the corresponding Methoxy Analog as described in Example 1E of published International Application WO 85/04307). In Examples 1-4, 6, 7 the Hydroxy Analog is treated to form the nitrophenyl (or nitropyridinyl) ether, which is then treated to form the hydroxyphenyl (or hydroxypyridinyl) ether, followed by etherification with the appropriate moiety. In Example 5, the Hydroxy Analog is treated to form the cyanophenyl ether after which the cyano group is converted to the desired substituent, in that case eventually an N-alkylsulfonylaminocarbonyl substituent. Other methods are illustrated below. In Method B the process is illustrated with a compound in which "M" is N instead of CH; in that method the hydroxypyridiyl ether is produced by treating the methoxypyridyl ether with BBr₃. In Method C the first step is an etherification to introduce the R² group followed by a reduction of the nitro substituent (on the Ar group) to form an amino group which is then converted to a chlorine substituent. Methods D and E relate to processes for making the Q'--Ar--NH₂ compound whose NH₂ group can then be converted to the final triazolinone moiety in a conventional manner. In Method D the NH₂ group has been acylated to protect it during the various reactions. In Method E that NH₂ group is introduced by nitration followed by reduction. While these methods are illustrated specifically with reagents chosen to form the product of Example 1 (or, in Method B, the corresponding pyridyl compound), it will be understood by those skilled in the art that analogous reactants may be used to form other compounds disclosed herein.

Method B: React 1-(4-chloro-2-fluoro-5-hydroxyphenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one first with sodium hydride (e.g. in N,N-dimethylformamide ["DMF"] followed by reaction with an appropriately substituted 5-methoxypyridine (e.g. 2-fluoro-or 2-chloro-5-methoxypyridine) to form 1-[4-chloro-2-fluoro-5-(5-methoxypyridin-2-yl) oxyphenyl]-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one. Then treat with boron tribromide (e.g. in methylene chloride) followed by reaction with an alkyl (e.g. ethyl) 2-bromopropionate (e.g. in the presence of potassium carbonate and acetone) to form the corresponding alkyl 2-[5-[2-chloro-4-fluoro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5 -oxo-1H-1,2,4-triazol-1-yl)phenoxy]-pyridin-2-yl]oxypropionate.

Method C: React 1-(2,5-difluoro-4-nitrophenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol -5(1H)-one with an alkyl (e.g. ethyl) 2-(4-hydroxyphenoxy)-propionate in the presence of a base (such as sodium hydride in N,N-dimethylformamide) to form the alkyl 2-[4-[4-fluoro-2-nitro-5(4-difluoromethyl-4,5 -dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]phenoxy]-propionate. Reduce the nitro group by hydrogenation (e.g. in ethanol with a catalytic amount of platinum oxide) to form the alkyl 2-[4-[2-amino-4-fluoro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]phenoxy]propionate. Then treat (as with sodium nitrite and hydrochloric acid, followed by copper (I) chloride) to form the corresponding alkyl 2-[2-chloro-4-fluoro-5-(4-difluoromethyl-4,5-dihydro -3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]phenoxy]-propionate. propionate.

Method D: React 4-chloro-2-fluoro-5-hydroxyacetanilide with 4-fluoronitrobenzene (e.g. by heating in the presence of a base, such as sodium hydride, and DMF) to form 4-chloro-2-fluoro-5-(4-nitrophenoxy)-acetanilide. Reduce the NO₂ group (as by hydrogenation in ethanol with a catalytic amount of platinum oxide) to form 5-(4-aminophenoxy)-4-chloro-2-fluoroacetanilide. Treat the latter (e.g. with sodium nitrite and sulfuric acid followed by copper (II) sulfate) to form 4-chloro-2-fluoro-5-(4-hydroxyphenoxy)acetanilide. Then react with an alkyl halide, such as methyl iodide (e.g. in the presence of potassium carbonate and acetone) to form the alkyl 4-chloro-2-fluoro-5-(4-methoxyphenoxy)acetanilide. Hydrolyze the latter (as with hydrochloric acid) to form the corresponding aniline, e.g. 4-chloro-2-fluoro-5-(4-methoxyphenoxy)aniline.

Method E: React 2,5-difluoronitrobenzene with 4-methoxyphenol (e.g. in the presence of a base, such as sodium hydride, and DMF) to form 5-fluoro-2-(4-methoxyphenoxy)nitrobenzene. Reduce the nitro group (as by hydrogenation in ethanol with a catalytic amount of platinum oxide) to form 5-fluoro-2-(4-methoxyphenoxy)-aniline. Nitrate the latter (as with nitric acid and sulfuric acid) to form 5-fluoro-2-(4-methoxyphenoxy)-4-nitroaniline. Treat the latter (e.g. first with sodium nitrite and hydrochloric acid followed by copper (I) chloride) to form 4-chloro-2-fluoro-5-(4-methoxyphenoxy)nitrobenzene. Reduce the nitro group (e.g. by hydrogenating in ethanol with a catalytic amount of platinum oxide) to form the corresponding 4-chloro-2-fluoro-5-(4-methoxyphenoxy)aniline.

The compounds of the present invention wherein Z is S may be prepared using the following method: ##STR7## The reaction of an appropriately substituted 1-(5-aminophenyl)-4,5-dihydro-1,2,4-triazol-5(1H)-one with aqueous sodium nitrite and hydrochloric acid followed by the addition of aqueous copper II chloride, acetic acid and sulfur dioxide produced the correspondingly substituted 1-(5-chlorosulfonylphenyl)-4,5-dihydro-1,2,4-triazol-5(1H)-one (III). Treatment of (III) with stannous chloride dihydrate in acetic acid and hydrogen chloride gas yielded the substituted 1-(5-thiohydroxyphenyl)-4,5-dihydro-1,2,4-triazol-5(1H)-one (IV). The reaction of (IV) with potassium t-butoxide in tetrahydrofuran and then with an appropriately substituted iodoanisole or substituted iodomethoxypyridine in ethylene glycol in the presence of a small amount of bis(bipyridine)nickel II bromide yielded the substituted 1-[5-(substituted-methoxyphenylthio)- or 1-[5-(substituted-methoxypyridinylthio)phenyl]-4,5-dihydro-1,2,4-triazol-5(1H)-one (V). Treatment of (V) with boron tribromide in methylene chloride produced the substituted 1-[5-(substituted-hydroxyphenylthio) or 1-[5-(substituted hydroxypyridinylthio)phenyl]-4,5-dihydro-1,2,4-triazol-5(1H)-one (VI). The reaction of (VI) with potassium carbonate, an appropriately substituted bromopropionate, and, if desired, a small amount of 1,4,7,10,13,16-hexaoxacyclooctadecane (18-crown-6) in N,N-dimethylformamide yielded a compound of formula I in which the Z group is S.

To prepare compounds of the present invention wherein Z is NH or alkyl amino the following method may be used: ##STR8## The reaction of an appropriately substituted 1-(5-aminophenyl)-4,5-dihydro-1,2,4-triazol-5(1H)-one with an appropriately substituted fluoronitrobenzene or pyridine and potassium carbonate in a solvent such as N,N-dimethylformamide or 1-methyl-2-pyrrolidinone would produce the correspondingly substituted 1-[5-(substituted-nitrophenylamino)-or 1-[5-(substituted-nitropyridylamino)-4,5-dihydro-1,2,4-triazol-5(1H)-one (VII). The reduction of the nitro group of compound (VII) to an amino group, compound (VIII), would be accomplished by using iron filings and acetic acid. Subsequent treatment of (VIII) with sodium nitrite in sulfuric acid then with aqueous copper (II) sulfate in xylene would produce the substituted 1-[5-(substituted hydroxyphenylamino)- or 1-[5-(substituted hydroxypyridylamino)-4,5-dihydro-1,2,4-triazol-5(1H)-one (IX). The reaction of (IX) with potassium carbonate and an appropriately substituted bromopropionate in a solvent such as N,N-dimethylformamide would yield a compound of formula (I) in which the Z group is NH or an alkylamino.

It will be understood that substituents present in the final product may be introduced at various stages. For instance in methods D and E the methoxy group may be converted to a Q' group such as a C₂ H₅ O--CO--CH(CH₃)--O-- group at a subsequent stage in the process, or the latter group may be introduced earlier, as by using ethyl 2-bromopropionate in place of the methyl iodide in Method D or by using ethyl 2-(4-hydroxyphenoxy)-propionate in place of the 4-methoxyphenol in Method E.

EXAMPLE 1 ETHYL 2-[4-[(2-CHLORO-4-FLUORO-5-(4-DIFLUOROMETHYL-4,5-DIHYDRO-3-METHYL-5-OXO-1H-1,2,4-TRIAZOL-1-YL)PHENOXY]PHENOXY]PROPIONATE Step A 1-[4-Chloro-2-fluoro-5-(4-nitrophenoxy)phenyl]-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one

To a stirred mixture of 0.91 g (0.019 mole) of sodium hydride in 30 mL of N,N-dimethylformamide was added slowly a solution of 5.50 g (0.019 mole) of 1-[4-chloro-2-fluoro-5-hydroxyphenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one in 30 mL of N,N-dimethylformamide. To this mixture was added 2.68 g (0.019 mole) of 4-fluoronitrobenzene. The resultant mixture was stirred at room temperature for approximately 18 hours and then was heated at 80° C. for one hour. The mixture was allowed to cool and was poured into ice water. The aqueous mixture was extracted with diethyl ether. The extract was dried over anhydrous magnesium sulfate and filtered. The filtrate was evaporated under reduced pressure to yield 6.0 g of 1-[4-chloro-2-fluoro-5-(4-nitrophenoxy)phenyl]-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one as a solid, m.p. 115°-117° C., Compound 4 of Table 1.

The nmr spectrum was consistent with the proposed structure.

Step B 1-[5-(4-Aminophenoxy)-4-chloro-2-fluorophenyl]-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5-(1H)-one

Hydrogenation of 5.80 g (0.015 mole) of 1-[4-chloro-2-fluoro-5-(4-nitrophenoxy)phenyl]-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one dissolved in 100 mL of ethanol in the presence of a catalytic amount (0.30 g) of platinum oxide produced 4.6 g of 1-[5-(4-aminophenoxy)-4-chloro-2-fluorophenyl]-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one as a solid, m.p. 133°-135° C., Compound 3 of Table 1.

The nmr spectrum was consistent with the proposed structure.

Step C 1-[4-Chloro-2-fluoro-5-(4-hydroxyphenoxy)-phenyl]-4-difluoromethyl-4,5-dihydro -3-methyl-1,2,4-triazol-5(1H)-one

While maintaining a temperature of 20° to 25° C., 4.4 g (0.011 mole) of 1-[5-(4-aminophenoxy)-4-chloro-2-fluorophenyl]-4-difluoromethyl-4,5-dihydro -3-methyl-1,2,4-triazol-5(1H)-one was added to 4.0 mL of stirred, concentrated sulfuric acid. To this was added a solution of 0.89 g (0.13 mole) of sodium nitrite dissolved in 6.0 mL of water, while continuing to maintain a temperature of about 20° C. After complete addition, the mixture was stirred at 20° C. for 30 minutes. This mixture was added through a glass tube to the bottom of a stirred, refluxing mixture of 32.0 g (0.13 mole) of copper (II) sulfate pentahydrate, 80 mL of water and 30 mL of xylene. After complete addition the mixture was refluxed for one hour. The mixture was cooled, and the organic phase was separated from the aqueous phase. The organic phase was extracted with an aqueous, sodium hydroxide solution (6.0 g of sodium hydroxide pellets dissolved in 250 mL of water). The basic extract was neutralized with concentrated hydrochloric acid, causing a precipitate to form. The solid was collected by filtration to yield 2.3 g of 1-[4-chloro-2-fluoro-5-(4-hydroxyphenoxy)phenyl]-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5-(1H)-one, m.p. 162°-162° C., Compound 2 of Table 1.

Step D Ethyl 2-[4-[(2-chloro-4-fluoro-5-(4-difluoromethyl-4,5-dihydro-3-methyl -5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]phenoxy]propionate

A stirred mixture of 0.60 g (0.0015 mole) of 1-[4-chloro-2-fluoro-5-(4-hydroxyphenoxy)phenyl]-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one, 0.54 g (0.0030 mole) of ethyl 2-bromopropionate, and 0.32 q (0.0023 mole) of potassium carbonate in 30 mL of acetone was heated at reflux for six days. The mixture was cooled and filtered. The filtrate was evaporated under reduced pressure leaving a residue. This residue was purified by column chromatography on silica gel, eluting with methylene chloride to yield 0.43 g of ethyl 1-[4-[(2-chloro-4-fluoro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo -1H-1,2,4-triazol-1-yl)phenoxy]-phenoxy]propionate as a solid, m.p. 128°-129° C., Compound 5 of Table 1.

The nmr spectrum was consistent with the proposed structure.

EXAMPLE 2 N-METHYLSULFONYL-2-[4-[2-CHLORO-4-FLUORO-5-(4-DIFLUOROMETHYL-4,5-DIHYDRO-3-METHYL -5-OXO-1H 1,2,4-TRIAZOL-1-YL)PHENOXY]PHENOXY]PROPIONAMIDE

In a manner similar to Step D of Example 1, the reaction of 0.60 g (0.0015 mole) of 1-[4-chloro-2-fluoro-5-(4-hydroxyphenoxy)phenyl]-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one, 0.32 g (0.0014 mole) of N-methylsulfonyl-2-bromopropionamide, and 0.24 g (0.0017 mole) of potassium carbonate in 20 mL of acetone produced 0.3 g of N-methylsulfonyl-2-[4-[2-chloro-4-fluoro-5-(4-difluoromethyl-4,5 -dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]phenoxy]-propionamide as an oil, Compound 32 of Table 1.

The nmr spectrum was consistent with the proposed structure.

EXAMPLE 3 METHYL 2-[2-[2-CHLORO-4-FLUORO-5-(4-DIFLUOROMETHYL-4,5-DIHYDRO-3-METHYL-5-OXO -1H-1,2,4-TRIAZOL-1-YL)PHENOXY]PYRIDIN-5-YLOXY]PROPIONATE Step A 1-[4-Chloro-2-fluoro-5-(5-nitropyridin-2-yloxy)phenyl]-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one

To a stirred mixture of 5.0 g (0.017 mole) of 1-(4-chloro-2-fluoro-5-hydroxyphenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one and 2.6 g (0.019 mole) of potassium carbonate in 25 mL of acetone was added 2.7 g (0.017 mole) of 2-chloro-5-nitropyridine. The mixture was stirred at room temperature for one hour, then was heated at reflux for two hours. The mixture was allowed to cool to room temperature and was stirred for approximately 18 hours. The reaction mixture was heated at reflux for an additional four hours, then cooled and stirred at room temperature for approximately 18 hours. The mixture was filtered, and the filtrate was evaporated under reduced pressure to leave an oily residue, which crystallized upon standing to give 7.0 g of 1-[4-chloro-2-fluoro-5-(5-nitropyridin-2-yloxy)phenyl]-4-difluoromethyl -4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one, m.p. 120°-123° C.

The nmr spectrum was consistent with the proposed structure.

Step B 1-[5-(5-Aminopyridin-2-yloxy)-4-chloro-2-fluorophenyl]-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one

Iron filings (3.6 g, 0.064 mole) were added slowly to a stirred mixture of 7.0 g (0.017 mole) of 1-[4-chloro-2-fluoro-5-(5-nitropyridin-2-yloxy) phenyl]-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one, 25 mL of glacial acetic acid, 12 mL of tetrahydrofuran, and 5 mL of water. The reaction mixture was stirred at room temperature for three hours and was then diluted with 20 mL of diethyl ether. The mixture was filtered through a pad of Celite® filter aid, and the filtrate was stored at 5° C. to 10° C. for approximately 18 hours. The filtrate was neutralized by the addition of solid sodium bicarbonate and water. The organic phase was separated from the aqueous phase. The aqueous phase was extracted several times with diethyl ether, and the extracts were combined with the organic phase. The combined organic phase was washed first with water, then with an aqueous, saturated sodium chloride solution. The organic phase was dried over anhydrous magnesium sulfate and filtered. The filtrate was evaporated under reduced pressure to yield 6.0 g of 1-[5-(5-aminopyridin-2-yloxy)-4-chloro-2-fluorophenyl]-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one as a solid.

Analysis of this compound by thin layer chromatography showed it to be the same as a previously prepared sample the melting point of which was 138°-140° C. and the nmr spectrum of which was consistent with the proposed structure.

Step C 2-[2-Chloro-4-fluoro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H -1,2,4-triazol-1-yl)phenoxy]pyridine-5-diazonium tetrafluoroborate

To a stirred mixture of 3.9 g (0.010 mole) of 1-[5-(5-aminopyridin-2-yloxy)-4-chloro-2-fluorophenyl]-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one in 10 mL of water was added 5.0 mL of concentrated hydrochloric acid. The mixture was cooled in an ice water bath, and a solution of 0.76 g (0.011 mole) of sodium nitrite in 1.4 mL of water was added portionwise. The resultant mixture was stirred at 0° C. for 30 minutes, and a solution of 1.5 g (0.014 mole) of sodium tetrafluoroborate in 5 mL of water was added portionwise. An additional 5 mL of water was added, and the reaction mixture was stirred at 0° C. for 45 minutes. The mixture was filtered, and the filter cake was rinsed with ice water followed by diethyl ether. The filter cake was dried under reduced pressure to yield 4.7 g of 2-[2-chloro-4 -fluoro-5-(4-difluoromethyl-4,5-dihydro -3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]pyridine-5-diazonium tetrafluoroborate.

Step D 1-[4-Chloro-2-fluoro-5-(5-hydroxypyridin-2-yloxy)phenyl]-4-difluoromethyl-4,5 -dihydro-3-methyl-1,2,4-triazol-5(1H)-one

To a stirred, cold (ice bath) solution of 0.67 g (0.0048 mole) of potassium carbonate in 20 mL of trifluoroacetic acid was added 4.7 g (0.097 mole) of 2-[2-chloro-4-fluoro-5-(4-difluoromethyl-4,5-dihydro -3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]pyridine-5-diazonium tetrafluoroborate. The reaction mixture was allowed to warm to room temperature and was then heated at reflux for 5.5 hours. The mixture was cooled to room temperature, diluted with 50 mL of water, and the whole was extracted with four portions of methylene chloride. The extracts were combined, dried over anhydrous magnesium sulfate, and filtered. The filtrate was evaporated under reduced pressure to give a red oil which was purified by column chromatography on silica gel. Elution with n-hexane:ethyl acetate (2:1) gave 3.3 g of 1-[4-chloro-2-fluoro-5-(5-hydroxypyridin-2-yloxy)-phenyl]-4-difluoromethyl-4,5-dihydro -3-methyl,1,2,4-triazol-5(1H)-one as a solid, m.p. 179°-181° C.

Step E Methyl 2-[2-[2-chloro-4-fluoro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5 -oxo-1H-1,2,4-triazol-1-yl)phenoxy]pyridin-5-yloxy]propionate

Under a dry nitrogen atmosphere, 0.28 g (0.0017 mole) of methyl 2-bromopropionate was added to a stirred solution of 0.60 g (0.0016 mole) of 1-[4-chloro-2-fluoro-5-(5-hydroxypyridin-2-yloxy)phenyl ]-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one and 0.32 g (0.0023 mole) of potassium carbonate in 10 mL of acetone. The reaction mixture was stirred at room temperature for one hour, then was heated at reflux for approximately 18 hours. The mixture was cooled to room temperature and was filtered. The filtrate was evaporated under reduced pressure leaving a residue which was purified by column chromatography on silica gel. Elution with n-hexane:ethyl acetate (1:1) gave 0.78 g of methyl 2-[2-[2-chloro-4-fluoro-5-(4-difluoro-methyl-4,5-dihydro-3-methyl -5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]pyridin-5-yloxy]propionate as a yellow oil.

The nmr and IR spectra were consistent with the proposed structure.

EXAMPLE 4 2-[2-[2-CHLORO-4-FLUORO-5-(4-DIFLUOROMETHYL-4,5-DIHYDRO-3-METHYL-5-OXO-1H -1,2,4-TRIAZOL-1-YL)PHENOXY]PYRIDIN-5-YLOXY]PROPIONIC ACID

A mixture of 1.2 g (0.0023 mole) of t-butyl 2-[2-[2-chloro-4-fluoro-5-(4-difluoromethyl -4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]pyridin-5-yloxy]propionate (prepared by the method of Example 3, Step E using t-butyl 2-chloropropionate) in 7 mL of trifluoroacetic acid was stirred at room temperature for 30 minutes. The excess trifluoroacetic acid was removed by evaporation under reduced pressure leaving an oil. The oil was partitioned between diethyl ether and water. The organic phase was separated, dried over anhydrous magnesium sulfate, and filtered. The filtrate was evaporated under reduced pressure leaving a thick oil. Upon standing, the oil crystallized as a white solid. The solid was triturated with petroleum ether to give 0.66 g of 2-[2-[2-chloro-4-fluoro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]pyridin-5-yloxy]propionic acid, m.p. 49°-51° C.

The nmr and IR spectra were consistent with the proposed structure.

EXAMPLE 5 N-(1-METHYLETHYL)SULFONYL-4-[2-CHLORO-4-FLUORO-5-(4-DIFLUOROMETHYL-4,5-DIHYDRO-3-METHYL-5-OXO-1H-1,2,4-TRIAZOL-1-YL)PHENOXY]PHENYLCARBOXAMIDE Step A 1-[4-Chloro-5-(4-cyanophenoxy)-2-fluorophenyl]-4-difluoromethyl-4,5-dihydro -3-methyl-1,2,4-triazol-5(1H)-one

To a stirred solution of 5.0 g (0.017 mole) of 1-(4-chloro-2-fluoro-5-hydroxyphenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one in 150 mL of N,N-dimethylformamide was added 2.8 g (0.020 mole) of potassium carbonate. The resultant mixture was stirred for ten minutes, and 2.1 g (0.017 mole) of 4-fluorobenzonitrile was added. The mixture was stirred and heated at 120° C. for approximately 18 hours. The solvent was removed from the mixture by distillation under reduced pressure leaving a residue which was partitioned between diethyl ether and water. The organic phase was separated, dried over anhydrous magnesium sulfate, and filtered. The filtrate was evaporated under reduced pressure to give 4.4 g of 1-[4-chloro-5-(4-cyanophenoxy)-2-fluorophenyl]-4-difluoromethyl -4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one as a solid.

A previously prepared sample of this compound, prepared in the manner described above, had a melting point of 175°-177° C. and an nmr spectrum which was consistent with the proposed structure.

Step B Methyl 4-[2-chloro-4-fluoro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo -1H-1,2,4-triazol-1-yl)phenoxy]phenylcarboxylate

A solution of 4.4 g (0.011 mole) of 1-[4-chloro-5-(4-cyanophenoxy)-2-fluorophenyl]-4-diffluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one in 200 mL of methanol was stirred at room temperature while gaseous hydrogen chloride was bubbled into the solution. After approximately 15 minutes, the hydrogen chloride flow was stopped, and the reaction mixture was heated at reflux for approximately 18 hours. Additional hydrogen chloride gas was bubbled into the reaction mixture two more times during a three day period, the mixture being cooled during addition and heated following addition. The reaction mixture was cooled, and the solvent was removed by evaporation under reduced pressure leaving a residue. The residue was partitioned between diethyl ether and water. The organic phase was separated, dried over anhydrous magnesium sulfate, and filtered. The filtrate was evaporated under reduced pressure leaving an oil. The oil was purified by column chromatography on silica gel, eluting with n-heptane:ethyl acetate (85:15) to give 1.8 g of methyl 4-[2-chloro-4-fluoro-5-(4-difluoromethyl-4,5-dihydro -3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]phenylcarboxylate as a solid, m.p. 97°-98° C., Compound 126 of Table 1.

The nmr and IR spectra were consistent with the proposed structure.

Step C 4-[2-Chloro-4-fluoro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H -1,2,4-triazol-1-yl)phenoxy]phenylcarboxylic acid

To a stirred mixture of 1.8 g (0.0042 mole) of methyl 4-[2-chloro-4-fluoro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4 -triazol-1-yl)phenoxy]-phenylcarboxylate and 1.3 g (0.0029 mole) of ethyl 4-[2-chloro-4-fluoro-5-(4-difluoromethyl-4,5-dihydro -3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]phenylcarboxylate (prepared by the method of Step B using ethanol in place of methanol) in 20 mL of tetrahydrofuran was added a solution of 0.58 g (0.014) of sodium hydroxide in 30 mL of water. The reaction mixture was heated at 50° C. for 1.5 hour, then was stirred at room temperature for approximately 18 hours. The mixture was again heated at 50° C. for two hours and then was allowed to cool. The solvent was removed from the mixture by evaporation under reduced pressure leaving a residue. The residue was stirred in a 2N hydrochloric acid solution, and the resultant mixture was extracted successively with diethyl ether and ethyl acetate. The organic phases were combined, dried over anhydrous magnesium sulfate, filtered, and the filtrate concentrated under reduced pressure to give a solid residue. The residue was purified by column chromatography on silica gel, eluting with methylene chloride:methanol (95:5) to give 2.5 g of 4-[2-chloro-4-fluoro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo 1H-1,2,4-triazol-1-yl)phenoxy]phenylcarboxylic acid as a solid, m.p. 184°-185° C.

Step D 4-[2-Chloro-4-fluoro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H -1,2,4-triazol-1-yl)phenoxy]phenylcarboxylic acid chloride.

A stirred solution of 1.7 g (0.0041 mole) of 4-[2-chloro-4-fluoro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]phenylcarboxylic acid in 75 mL of thionyl chloride was heated at reflux for four hours. The excess thionyl chloride was removed by distillation under reduced pressure to yield 4-[2-chloro-4-fluoro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]-phenylcarboxylic acid chloride as a yellow oil.

Step E N-(1-Methylethyl)sulfonyl-4-[2-chloro-4-fluoro-5-(4-difluoromethyl-4,5-dihydro -3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]phenylcarboxamide

A stirred mixture of 0.59 g (0.0014 mole) of 4-[2-chloro-4-fluoro-5-(4-difluoromethyl -4,5-dihydro-3-methyl-5-oxo-1H-1,2,4 triazol-1-yl)phenoxy]phenyl-carboxylic acid chloride and 0.17 g (0.0014 mole) of 2-sulfamylpropane was heated at 195° C. for approximately 15 minutes. The mixture was cooled and 2 mL of methylene chloride was added. The mixture was allowed to stand at room temperature for approximately 18 hours. A brown solid formed, was collected and triturated with petroleum ether. Recovery of the solid by filtration gave 0.58 g of N-(1-methylethyl)sulfonyl-4-[2-chloro-4-fluoro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]phenylcarboxamide as a solid, m.p. 185°-187° C., Compound 130 of Table 1.

The nmr and IR spectra were consistent with the proposed structure.

EXAMPLE 6

1-[2,4-DICHLORO-5-(4-NITROPHENOXY)PHENYL]-4-DIFLUOROMETHYL-4,5-DIHYDRO-3-METHYL -1,2,4-TRIAZOL-5-(1H)-ONE

A stirred mixture of 1.0 g (0.0032 mole) of 1-(2,4-dichloro-5-hydroxyphenyl)-4-difluoromethyl -4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one, 0.66 g (0.0048 mole) of potassium carbonate, and 0.76 g (0.0048 mole) of 4-chloronitrobenzene in 20 ml of N,N-dimethylformamide was heated at 120° C. for approximately 18 hours. The reaction mixture was cooled and was poured into ice-water. This aqueous mixture was neutralized with hydrochloric acid and then was extracted with ethyl acetate. The organic phase was washed with water and then was dried over anhydrous magnesium sulfate. This mixture was filtered, and the filtrate was evaporated under reduced pressure leaving an orange oil. The orange oil was purified by column chromatography on silica gel, eluting with methylene chloride to yield 1.2 g of 1-[2,4-dichloro-5-(4-nitrophenoxy)phenyl]-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one as a solid, m.p. 99°-101° C., compound 92 of Table 1.

The nmr and ir spectra were consistent with the proposed structure.

EXAMPLE 7 METHYL 2-[4-[2,4-DICHLORO-5-(4-DIFLUOROMETHYL-4,5-DIHYDRO-3-METHYL-5-OXO -1H-1,2,4-TRIAZOL-1-YL)PHENOXY]-3-CHLOROPHENOXY]-PROPIONATE Step A 1-[2,4-Dichloro-5-(2-chloro-4-nitrophenoxy)-phenyl]-4-difluoromethyl-4,5-dihydro -3-methyl-1,2,4-triazol-5-(1H)-one

A mixture of 10.0 g (0.032 mole) of 1-(2,4-dichloro-5-hydroxyphenyl)-4-difluoromethyl-4,5-dihydro -3-methyl-1,2,4-triazol-5(1H)-one, 5.52 g (0.040 mole) of potassium carbonate, and 7.02 g (0.040 mole) of 3-chloro-4-fluoronitrobenzene in 60 ml of N,N-dimethylformamide was stirred at room temperature for approximately 18 hours. The reaction mixture was poured into ice-water. This aqueous mixture was extracted with diethyl ether. The extract :;as dried over anhydrous magnesium sulfate and was filtered. The filtrate was evaporated under reduced pressure leaving a residue. This residue was purified by column chromatography on silica gel to yield 10.4 g of 1-[2,4-dichloro-5-(2-chloro-4-nitrophenoxy)phenyl]-4-difluoromethyl -4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one as a solid, m.p. 135°-135.5° C., compound 179 of Table 1.

The nmr spectrum was consistent with the proposed structure.

1-[5-(4-Amino-2-chlorophenoxy)-2,4-dichlorophenyl]-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one

To a stirred mixture of 10.0 g (0.021 mole) of 1-[2,4-dichloro-5-(2-chloro-4-nitrophenoxy) phenyl]-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one in 100 ml of glacial acetic acid and 5 ml of water was added slowly 10.0 g (0.179 mole) of iron powder. The reaction mixture was heated at 50° C. and then was allowed to cool to room temperature at which it was stirred for 1.5 hours. The mixture was poured into ice-water, and the aqueous mixture was extracted with diethyl ether. The extract was evaporated under reduced pressure leaving a residue. This residue was purified by column chromatography to yield 8.5 g of 1-[5-(4-amino-2-chlorophenoxy)-2,4-dichlorophenyl]-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one as a solid, m.p. 161°-162° C., compound 180 of Table 1.

Step C 1-[2,4-Dichloro-5-(2-chloro-4-hydroxyphenoxy)-phenyl]- 4-difluoromethyl-4,5-dihydro -3-methyl-1,2,4-triazol-5(1H)-one

In a manner similar to Step C of Example 1, 8.10 g (0.0186 mole) of 1-[5-(4-amino-2-chlorophenoxy)-2,4-dichlorophenyl]-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one in 60 ml of concentrated sulfuric acid was reacted with a solution of 1.30 g (0.019 mole) of sodium nitrite in 10 ml of water. Subsequent reaction of this mixture with a refluxing solution of 150.0 g (0.60 mole) of copper (II) sulfate pentahydrate in 150 ml of water and 1.50 ml of xylene yielded 2.6 g of 1-[2,4-dichloro-5-(2-chloro-4-hydroxyphenoxy)phenyl]-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one, compound 181 of Table 1.

Step D Methyl 2-[4-[2,4-dichloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo -1H-1,2,4-triazol-1-yl)phenoxy]-3-chlorophenoxy]propionate

In a manner similar to Step D of Example 1, the reaction of 1.3 g (0.0029 mole) of 1-[2,4-dichloro-5-(2-chloro-4-hydroxyphenoxy)phenyl]-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one with 0.73 g (0.0044 mole) of methyl 2-bromopropionate and 0.60 g (0.0044 mole) of potassium carbonate in 60 ml of methyl ethyl ketone yielded 0.78 g of methyl 2-[4-[2,4-dichloro-5-(4-difluoromethyl-4,5-dihydro -3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]-3-chlorophenoxy]propionate as an oil, compound 150 of Table 1.

EXAMPLE 8 METHYL 2-[4-[2,4-DICHLORO-5-(4-DIFLUOROMETHYL-4,5-DIHYDRO-3-METHYL-5-OXO-1H -1,2,4-TRIAZOL-1-YL)PHENYLTHIO]PHENOXY]PROPIONATE Step A 1 (2,4-Dichloro-5-chlorosulfonylphenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one

A stirred mixture of 12.0 g (0.0388 mole) of 1-(5-amino-2,4-dichlorophenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one in 50 mL of hydrochloric acid was cooled to 0° C. A solution of 2.79 g (0.0405 mole) of sodium nitrite in 20 mL of water was added while maintaining a reaction temperature of approximately 0° C. After complete addition, the reaction mixture was allowed to warm to room temperature and stir for 1.5 hours. This mixture was added slowly to a solution of 5.44 g (0.0405 mole) of copper (II) chloride in 15 mL of water and 50 mL of acetic acid which was saturated with sulfur dioxide. The resultant mixture was stirred at room temperature for one hour, forming a precipitate. The reaction mixture was poured into ice water and was stirred for a brief period of time. This mixture was filtered to collect approximately 16 grams of 1-(2,4-dichloro-5-chlorosulfonylphenyl)-4-difluoromethyl-4,5-dihydro-3-methyl -1,2,4-triazol-5(1H)-one as an off-white solid.

Step B 1-(2,4-Dichloro-5-thiohydroxyphenyl)-4-difluoromethyl-4,5-dihydro-3-methyl -1,2,4-triazol-5(1H)-one

Under a dry nitrogen atmosphere, a mixture of 26.4 g (0.117 mole) of stannous chloride dihydrate in 100 mL of acetic acid was stirred while hydrogen chloride gas was bubbled into the mixture. During this process, the mixture became a colorless solution (approximately five minutes), and the addition of hydrogen chloride gas was stopped. This solution was heated at 85° C., and a hot solution of 15.0 g (0.0388 mole) of 1-(2,4-dichloro-5-chlorosulfonylphenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one in 60 mL of acetic acid was added. The resultant mixture was heated at 85° C. for 30 minutes. The reaction mixture was allowed to cool and was poured into 150 mL of hydrochloric acid. An aqueous, saturated solution of sodium chloride (120 mL) was added, and the resultant mixture was extracted three times with ethyl acetate. The organic extracts were combined and washed in succession with three portions of water and an aqueous, saturated sodium chloride solution. The washed organic phase was dried over anhydrous magnesium sulfate and was filtered. The filtrate was evaporated under reduced pressure, leaving a yellow solid. This solid was purified by column chromatography on silica gel to yield 4.85 grams of 1-(2,4-dichloro-5-thiohydroxyphenyl)-4-difluoromethyl -4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one as a solid. The nmr spectrum was consistent with the proposed structure.

Step C 1-[2,4-Dichloro-5-(4-methoxyphenylthio)phenyl]-4-difluoromethyl-4,5-dihydro-3-methyl -1,2,4-triazol-5(1H)-one

A solution of 4.85 g (0.0147 mole) of 1-(2,4-dichloro-5-thiohydroxyphenyl)-4-difluoromethyl -4,5-dihydro-3-methyl 1,2,4-triazol-5(1H)-one and 1.67 g (0.0149 mole) of potassium t-butoxide in 30 mL of tetrahydrofuran was stirred at room temperature for ten minutes. The solvent was removed from the reaction mixture by evaporation under reduced pressure, leaving a brown solid residue. To this: residue was added 50 mL of ethylene glycol, 0.05 g (1.3 x 10-4 mole) of bis-(bipyridine)nickel (II) bromide (prepared by the method of Cristau, et al., Organometallics, 4, 657-661, 1985), and 5.27 g (0.0224 mole) of 4-iodoanisole. This mixture was stirred and heated at 120° C. for approximately 65 hours. The reaction mixture was allowed to cool and was diluted with diethyl ether. This mixture was washed with three portions of water. The organic phase was dried over anhydrous magnesium sulfate and was filtered. The filtrate was evaporated under reduced pressure, leaving a purple oil. This oil was purified by column chromatography on silica gel, eluting with methylene chloride:petroleum ether (1:2) to yield 2.0 g of 1-[2,4-dichloro-5-(4-methoxyphenylthio)phenyl]-4-difluoro-methyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one as a solid, m.p. 134°-137° C. The nmr spectrum was consistent with the proposed structure.

Step D 1-[2,4-Dichloro-5-(4-hydroxyphenylthio)phenyl]-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one

A solution of 2.5 g (0.0058 mole) of 1-[2,4-dichloro-5-(4-methoxyphenylthio)phenyl]-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one in 30 mL of methylene chloride was added slowly to 11.6 mL of a cold (-20° C.), stirred solution of one molar boron tribromide in methylene chloride. After complete addition, the reaction mixture was allowed to warm to room temperature and stir for approximately 18 hours. The reaction mixture was poured into ice-water forming a precipitate. This white solid was isolated by filtration; m.p. 230°-231° C. An nmr spectrum indicated that this was the desired product, 1-[2,4-dichloro-5-(4-hydroxyphenylthio)phenyl]-4-difluoromethyl -4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one. The filtrate was washed with water, and the organic phase was evaporated under reduced pressure, leaving a brown solid. This brown solid was washed in succession with methylene chloride, diethyl ether, and ethyl acetate, leaving a white solid. Analysis of this solid by nmr spectroscopy indicated that it was product, m.p. 228°-229° C. The organic filtrates from washing the brown solid were combined and analyzed by thin layer chromatography. This analysis indicated product was present, and that product was removed by column chromatography on silica gel, eluting with diethyl ether:petroleum ether (1:1). A solid fraction obtained from this process was identified as product by nmr spectroscopy.

All solids which were identified as product were combined to yield 2.1 grams of 1-[2,4-dichloro-5-(4-hydroxyphenylthio)phenyl]-4-difluoromethyl -4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one.

Step E Methyl 2-[4-[2,4-dichloro-5-(4-difluoro-methyl-4,5-dihydro-3-methyl-5-oxo -1H-1,2,4-triazol-1-yl)phenylthio]phenoxy]-propionate

A stirred mixture of 1.5 g (0.0036 mole) of 1-[2,4-dichloro-5-(4-hydroxyphenylthio)phenyl]-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one, 0.75 g (0.0054 mole) of potassium carbonate, 0.90 g (0.0054 mole) of methyl DL-2-bromopropionate, and 0.20 g (8×10⁻⁴ mole) of 18-crown-6 in 30 mL of N,N-dimethylformamide was heated at 100°-120° C. for approximately 18 hours. The reaction mixture was allowed to cool and was poured into ice-water. This aqueous mixture was extracted with diethyl ether and ethyl acetate. The organic extracts were combined and washed with water. The organic phase was dried over anhydrous magnesium sulfate and was filtered. The filtrate was evaporated under reduced pressure, leaving a yellow oil. This oil was purified by column chromatography on silica gel, eluting with diethyl ether:petroleum ether (40:60) to yield 0.83 g of methyl 2-[4-[2,4-dichloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl- 5-oxo-1H-1,2,4-triazol-1-yl)phenylthio]phenoxy]propionate as a solid, m.p. 100°-101° C. The nmr spectrum was consistent with the proposed compound.

EXAMPLE 9 1-[5-(4-AMINOPHENYL)AMINO-2,4-DICHLOROPHENYL]-4-DIFLUOROMETHYL-4,5-DIHYDRO-3-METHYL -1,2,4-TRIAZOL-5(1H)-ONE Step A 1-[2,4-Dichloro-5-(4-nitrophenyl)aminophenyl]-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one

To a stirred, cold (0° C.) mixture of 0.085 gram (0.00355 mole) of sodium hydride in 10 mL of N,N-dimethylformamide was added 1.0 gram (0.00323 mole) of 1-(5-amino-2,4-dichlorophenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one. After stirring for a brief period of time, 0.455 gram (0.00323 mole) of 4-fluoronitrobenzene was added. The resultant mixture was allowed to warm to room temperature and was stirred for one hour. The reaction mixture was heated at 60° C. for three hours and an additional 0.455 gram of 4-fluoronitrobenzene was added. This mixture was heated at 50° C. for approximately 18 hours. After cooling to room temperature, the mixture was poured into ice water. The aqueous mixture was extracted with three portions of ethyl acetate. The extracts were combined and washed in succession with 1N hydrochloric acid, an aqueous saturated sodium bicarbonate solution, water, and an aqueous sodium chloride solution. The washed organic phase was dried over anhydrous magnesium sulfate and was filtered. The filtrate was evaporated under reduced pressure to yield a solid. This solid was purified by recrystallization from ethyl acetate and n-heptane to yield 0.25 gram of 1-[2,4-dichloro-5-(4-nitrophenyl)-aminophenyl]-4-difluoromethyl-4,5-dihydro -3-methyl-1,2,4-triazol-5(1H)-one, m.p. 249°-251° C. The mother liquor from the recrystallization process was evaporated under reduced presure leaving 1.0 gram of an orange oil. Analysis of this oil by thin layer chromatography indicated it contained a substantial amount of the desired product.

Step B 1-[5-(4-Aminophenyl)amino-2,4-dichlorophenyl]-4-difluoromethyl-4,5-dihydro-3-methyl -1,2,4-triazol-5(1H)-one

The hydrogenation of 1.0 gram of the orange oil from Step A with approximately 0.01 gram of platinum oxide in 50 mL of ethyl acetate produced an oil. This oil was purified by chromatography or a 4 mm Chromatatron® chromatography plate to yield 0.17 gram of 1-[5-(4-aminophenyl)amino-2,4-dichlorophenyl]-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one as a solid, m.p. 196°-197° C. The nmr spectrum was consistent with the proposed structure.

Other compounds of the invention may be prepared by the methods exemplified above or by methods within the skill of the art.

HERBICIDAL ACTIVITY

The plant test species used in demonstrating the herbicidal activity of compounds of this invention include cotton (Gossypium hirsutum var. Stoneville), soybean (Glycine max var. Williams), field corn (Zea mays var. Agway 595S), wheat (Triticum aestivium var. Prodax), rice (Oryza sativa var. Labelle), morningglory (Ipomea lacunosa or Ipomea hederacea), velvetleaf (Abutilon theophrasti), barnyardgrass (Echinochloa crus galli), green foxtail (Setaria viridis), johnsongrass (Sorghum halepense), and wild mustard (Brassica raber).

Seeds or tubers of the plant test species were planted in furrows in steam sterilized sandy loam soil contained in disposable fiber flats. A topping soil of equal portions of sand and sandy loam soil was placed uniformly on top of each flat to a depth of approximately 0.5 cm.

The flats for the preemergence test were watered, then drenched with the appropriate amount of a solution of the test compound in a mixture of acetone and water containing a small amount (up to 0.5% v/v) of sorbitan monolaurate emulsifier/solubilizer. The concentration of the test compound in solution was varied to give a range of application rates, generally 8.0 kg/ha and submultiples thereof. The flats were placed in a green-house and watered regularly at the soil surface for 21 days at which time phytotoxicity data were recorded.

The flats for the postemergence test were placed in a greenhouse and watered for 8-10 days, then the foliage of the emerged test plants was sprayed with a solution of the test compound in acetone-water containing up to 0.5% sorbitan monolaurate. After spraying the foliage was kept dry for 24 hours, then watered regularly for 21 days, and phytotoxicity data recorded.

Herbicidal data at selected application rates are given for various compounds of the invention in Tables 3, 3A, 3B, 3C, 4 and 4A, 4B, 4C below. The test compounds are identified therein by numbers which correspond to those in Tables: 1, 1A, 1B, and 1C .

In Tables 3, 3A, 3B, 3C, 4, 4A, 4B, and 4C below:

"kg/ha" is kilograms per hectare, and

"% C" is percent control.

For herbicidal application, the compound is formulated into herbicidal compositions, by admixture, in herbicidally effective amounts, with adjuvants and carriers normally employed in the art for facilitating the dispersion of active ingredients for the particular utility desired, recognizing the fact that the formulation and mode of application of a toxicant may affect the activity of the material in a given application. Thus, for agricultural use the present herbicidal compounds may be formulated as granules of relatively large particle size, as water-soluble or water-dispersible granules, as powdery dusts, as wettable powders, as emulsifiable concentrates, as solutions, or as any of several other known types of formulations, depending on the desired mode of application.

For preemergence application these herbicidal compositions are usually applied either as sprays, dusts, or granules in the areas in which suppression of vegetation is desired. For postemergence control of established plant growth, sprays or dusts are most commonly used. These formulations may contain as little as 0.5% to as much as 95% or more by weight of active ingredient.

Dusts are free flowing admixtures of the active ingredient with finely divided solids such as talc, natural clays, kieselguhr, flours such as walnut shell and cottonseed flours, and other organic and inorganic solids which act as dispersants and carriers for the toxicant; these finely divided solids have an average particle size of less than about 50 microns. A typical dust formulation useful herein is one containing 1.0 part of the herbicidal compound and 99.0 parts of talc.

Wettable powders, also useful formulations for both pre- and postemergence herbicides, are in the form of finely divided particles which disperse readily in water or other dispersant. The wettable powder is ultimately applied to the soil either as a dry dust or as an emulsion in water or other liquid. Typical carriers for wettable powders include Fuller's earth, kaolin clays, silicas, and other highly absorbent, readily wet inorganic diluents. Wettable powders normally are prepared to contain about 5-80% of active ingredient, depending on the absorbency of the carrier, and usually also contain a small amount of a wetting, dispersing or emulsifying agent to facilitate dispersion. For example, a useful wettable powder formulation contains 80.8 parts of the herbicidal compound, 17.9 parts of Palmetto clay, and 1.0 part of sodium lignosulfonate and 0.3 part of sulfonated aliphatic polyester as wetting agents. Frequently, additional wetting agent and/or oil will be added to the tank-mix for postemergence application to facilitate dispersion on the foliage and absorption by the plant.

Other useful formulations for herbicidal applications are emulsifiable concentrates. Emulsifiable concentrates are homogeneous liquid compositions dispersible in water or other dispersant, and may consist entirely of the herbicidal compound and a liquid or solid emulsifying agent, or may also contain a liquid carrier, such as xylene, heavy aromatic naphthas, isophorone, or other non-volatile organic solvent. For herbicidal application these concentrates are dispersed in water or other liquid carrier, and normally applied as a spray to the area to be treated. The percentage by weight of the essential active ingredient may vary according to the manner in which the composition is to be applied, but in general comprises 0.5 to 95% of active ingredient by weight of the herbicidal composition.

Typical wetting, dispersing, or emulsifying agents used in agricultural formulations include, for example, the alkyl and alkylaryl sulfonates and sulfates and their sodium salts, polyhydric alcohols, and other types of surface active agents, many of which are available in commerce. The surface active agent, when used, normally comprises 1% to 15% by weight of the herbicidal composition.

Other useful formulations for herbicidal applications include simple solutions of the active ingredient in a solvent in which it is completely soluble at the desired concentration, such as acetone, alkylated naphthalenes, xylene, or other organic solvents. Granular formulations, wherein the toxicant is carried on relatively coarse particles, are of particular utility for aerial distribution or for penetration of cover crop canopy. Pressurized sprays, typically aerosols wherein the active ingredient is dispersed in finely divided form as a result of vaporization of a low boiling dispersant solvent carrier, such as the Freon® fluorinated hydrocarbons, may also be used. Water-soluble or water-dispersible granules are also useful formulations for herbicidal application of the present compounds. Such granular formations are free-flowing, non-dusty, and readily water-soluble or water-miscible. The soluble or dispersible granular formulations described in U.S. Pat. No. 3,920,442 are useful herein with the present herbicidal compounds.

The active herbicidal compounds of this invention may be formulated and/or applied with insecticides, fungicides, nematicides, plant growth regulators, fertilizers, or other agricultural chemicals and may be used as effective soil sterilants as well as selective herbicides in agriculture. In applying an active compound of this invention, whether formulated alone or with other agricultural chemicals, an effective amount and concentration of the active compound is of course employed; the amount may be as low as, for example, 2 g/ha or lower, e.g. about 1 to 250 g/ha preferably about 4 to 30 g/ha.

Compounds of this invention in which R² is R³ [CO--CH(R⁴)--O]_(n) -- or NCCH(R⁴)O--[CO--CH(R⁴)--O]_(m) -- are particularly suitable for "total vegetation control", i.e. control of emerged weeds in situations where residual herbicidal soil activity is undesirable. Thus, these compounds are highly effective when applied at low dosages to existing weed foliage, the dosages being such that the herbicide has little or no residual soil activity. This makes it possible for the farmer to plant seeds (or seedlings) safely within a short time (such as 3 to 7 days) before or after the application of the herbicide. Consequently, these herbicides are very suitable for clearing fields of weeds in the well known "no till" (or "reduced till", or "conservation till") farming methods, in which the soil is not tilled, or is tilled only in spaced, very narrow, seed-receiving rows (such as rows about an inch wide) before the crop seeds are planted. The absence of substantial residual herbicidal soil activity also makes these compounds very suitable for clearing weeds between existing crop plants, e.g. on plantations such as rubber, oil palm, banana or cocoa plantations, or on vineyards or orchards, such as in the interspaces and around the bases of trees and vines. The herbicides are also suitable for use as foliar-applied, pre-harvest crop desiccants, e.g. for treating mature cotton, potato, soybean or sunflower plants. For many of these uses the present commercially available herbicides are paraquat and glyphosate. The herbicides of this invention are superior to those materials in that they are effective at much lower rates of application, are less toxic, and are more effective on broadleaf weeds.

For "total vegetation control", as described above, the compounds of the invention may be applied in an effective amount and concentration; the amount may be as low as about 1 to 250 g/ha, preferably about 30 to 250 g/ha. For example, in no-till or reduced till farming, the following approximate rates of application may be used for the following compounds:

compound no. 5: 30 to 125 g/ha;

compound no. 7: 30 to 125 g/ha;

compound no. 149: 63 to 250 g/ha;

compound no. 113: 63 to 250 g/ha; and

compound no. 54: 30 to 125 g/ha.

The compounds in which R² is R³ [CO--CH(R⁴)--O]_(n) -- or NCCH(R⁴)O--]CO--CH(R⁴)--O]_(m) -- may be supplied in various types of formulations. The compounds may be sold to the user as emulsifiable concentrates which the user dilutes with water before spraying. As described earlier in this application, the emulsifiable concentrates are liquid compositions dispersible in water and may contain a liquid carrier (such as heavy aromatic naphtha) or may contain suspended solid herbicidal compound without such a carrier; in the latter case the concentrates are usually termed "flowable concentrates". Some of the foregoing compounds (such as compounds nos. 5, 7 and 82) are solids which are only slightly soluble (e.g. solubility less than 5%, such as less than 3%) in the usual aromatic solvents used as carriers in emulsifiable concentrates. It is therefore preferred to formulate the slightly soluble herbicidal compounds in the form of flowable concentrates containing very fine suspended particles (e.g. particles of average particle size less than 10 microns, such as 3 to 5 microns or less). Typical flowable concentrates may have formulations along the following lines:

    ______________________________________                                         Component:             % by Wt.                                                ______________________________________                                         Active ingredient      46.00                                                   Colloidal magnesium aluminum silicate                                                                 0.40                                                    Sodium alkylnaphthalenesulfonate                                                                      2.00                                                    Paraformaldehyde       0.10                                                    Water                  40.70                                                   Propylene glycol       7.50                                                    Acetylenic alcohols    2.50                                                    Xanthan gum            0.80                                                    Total                  100.00                                                  Active ingredient      45.00                                                   Water                  48.50                                                   Purified smectite clay 2.00                                                    Xanthan gum            0.50                                                    Sodium alkylnaphthalenesulfonate                                                                      1.00                                                    Acetylenic alcohols    3.00                                                    Total                  100.00                                                  ______________________________________                                    

The relatively insoluble compounds may also be supplied as solutions in such polar water-miscible solvents as N-methyl pyrrolidone; such solutions are then diluted with water and used for spraying without delay.

The more soluble compounds (such as compounds 54, 149 and 174) may be supplied as emulsifiable concentrates, as well as in the form of flowable concentrates. Typical emulsifiable concentrates may have formulations along the following lines:

    ______________________________________                                         Component:            % by Wt.                                                 ______________________________________                                         Active ingredient     53.01                                                    Blend of alkylnaphthalenesulfonate                                                                   6.00                                                     and polyoxyethylene ethers                                                     Epoxidized soybean oil                                                                               1.00                                                     Xylene                39.99                                                    Total                 100.00                                                   Active ingredient     10.00                                                    Blend of alkylnaphthalenesulfonate                                                                   4.00                                                     and polyoxyethylene ethers                                                     Xylene                86.00                                                    Total                 100.00                                                   ______________________________________                                    

It has been found that the herbicidal action of the compounds which are sparingly soluble in aromatic hydrocarbons, as well as those which are readily soluble in such hydrocarbons, is considerably increased (especially as to control of grasses) when the composition being sprayed on the foliage contains a substantially non-volatile aliphatic oil (e.g. of the type known as a "crop oil concentrate" or "oil concentrate") as an adjuvant. Such an adjuvant may be a hydrocarbon oil or a vegetable oil. The oil may be added with the water used to dilute the concentrate for spraying. The amount of such oil may be for example, about 3/4 quart to 1 1/2 quarts per acre to be treated.

The active herbicidal compounds of this invention may be used in combination with other herbicides, e.g. they may be mixed with, say, an equal or larger amount of a known herbicide such as chloroacetanilide herbicide such as 2-chloro-N-(2,6-diethylphenyl)-N-(methoxymethyl)acetamide (alachlor), 2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)acetamide (metolachlor), and N-chloroacetyl-N-(2,6-diethylphenyl)-glycine (diethatyl-ethyl); benzothiadiazinone herbicides such as 3-(1-methylethyl)-(1H)-2,1,3-benzothiadiazin-4-(3H)-one-2,2-dioxide (bentazon); triazine herbicides such as 6-chloro-N-ethyl-N-(1-methylethyl)-1,3,5-triazine-2,4-diamine (atrazine), and 2-[4-chloro-6-(ethylamino)-1,3,5-triazin-2-yl]amino-2-methylpropane-nitrile (cyanazine); dinitrolaniline herbicides such as 2,6-dinitro-N,N-dipropyl-4-(trifluoromethyl)benzeneamine (trifluralin); aryl urea herbicides such as N'-(3,4-dichlorophenyl)-N,N-dimethylurea (diuron) and N,N-dimethyl-N'-[3-(trifluoromethyl)phenyl]urea (fluometuron); and 2-[(2-chlorophenyl)methyl]-4,4-dimethyl-3-isoxazolidinone.

It is apparent that various modifications may be made in the formulation and application of the compounds of this invention without departing from the inventive concepts herein as defined in the claims.

                                      TABLE 1                                      __________________________________________________________________________      ##STR9##                                                                      Cmpd No.                                                                             R.sup.a R.sup.b                                                                              R.sup.2               R'     X  Y                          __________________________________________________________________________     1     CHF.sub.2                                                                              CH.sub.3                                                                             4-NO.sub.2            3-CN   F  Cl                         2     CHF.sub.2                                                                              CH.sub.3                                                                             4-OH                  H      F  Cl                         3     CHF.sub.2                                                                              CH.sub.3                                                                             4-NH.sub.2            H      F  Cl                         4     CHF.sub.2                                                                              CH.sub.3                                                                             4-NO.sub.2            H      F  Cl                         5     CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5                                                              H      F  Cl                         6     CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH.sub.2 CCH       H      F  Cl                         7     CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2 CH.sub.3                                                                     H      F  Cl                         8     CH.sub.3                                                                               CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2 CH.sub. 3                                                                    H      F  Cl                         9     CH(CH.sub.3).sub.2                                                                     CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2 CH.sub.3                                                                     H      F  Cl                         10    C.sub.2 H.sub.5                                                                        CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2 CH.sub.3                                                                     H      F  Cl                         11    CH.sub.2 CH.sub.2 CH.sub.2 F                                                           CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2 CH.sub.3                                                                     H      F  Cl                         12    CH.sub.2 CH.sub.2 F                                                                    CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2 CH.sub.3                                                                     H      F  Cl                         13    CH.sub.2 CH.sub.2 CH.sub.3                                                             CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2 CH.sub.3                                                                     H      F  Cl                         14    CH.sub.2 CHCH.sub.2                                                                    CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2 CH.sub.3                                                                     H      F  Cl                         15    CH.sub.2 CCH                                                                           CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2 CH.sub.3                                                                     H      F  Cl                         16    CHF.sub.2                                                                              Cl    4-OCH(CH.sub.3)CO.sub.2 CH.sub.3                                                                     H      F  Cl                         17    CHF.sub.2                                                                              Br    4-OCH(CH.sub.3)CO.sub.2 CH.sub.3                                                                     H      F  Cl                         18    CHF.sub.2                                                                              F     4-OCH(CH.sub.3)CO.sub.2 CH.sub.3                                                                     H      F  Cl                         19    CHF.sub.2                                                                              CH(CH.sub.3).sub.2                                                                   4-OCH(CH.sub.3)CO.sub.2 CH.sub.3                                                                     H      F  Cl                         20    CHF.sub.2                                                                              SCH.sub.3                                                                            4-OCH(CH.sub.3)CO.sub.2 CH.sub.3                                                                     H      F  Cl                         21    CHF.sub.2                                                                              SO.sub.2 CH.sub.3                                                                    4-OCH(CH.sub.3)CO.sub.2 CH.sub.3                                                                     H      F  Cl                         22    CHF.sub.2                                                                              SCF.sub.3                                                                            4-OCH(CH.sub.3)CO.sub.2 CH.sub.3                                                                     H      F  Cl                         23    CHF.sub.2                                                                              SO.sub.2 CF.sub.3                                                                    4-OCH(CH.sub.3)CO.sub.2 CH.sub.3                                                                     H      F  Cl                         24    CHF.sub.2                                                                              C.sub.2 H.sub.5                                                                      4-OCH(CH.sub.3)CO.sub.2 CH.sub.3                                                                     H      F  Cl                         25    CHF.sub.2                                                                              H     4-OCH(CH.sub.3)CO.sub.2 CH.sub.3                                                                     H      F  Cl                         26    CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2 H                                                                            H      F  Cl                         27    CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CONH.sub.2                                                                            H      F  Cl                         28    CHF.sub.3                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CONHCH.sub.3                                                                          H      F  Cl                         29    CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CON(CH.sub.3).sub.2                                                                   H      F  Cl                         30    CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CON(CH.sub.3)OCH.sub.3                                                                H      F  Cl                         31    CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CON(CH.sub.2 CHCH.sub.2).sub.2                                                        H      F  Cl                         32    CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CONHSO.sub.2 CH.sub.3                                                                 H      F  Cl                         33    CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CON(CH.sub.3)SO.sub.2 CH.sub.3                                                        H      F  Cl                         34    CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CON(C.sub.2 H.sub.5)SO.sub.                                                           H CH.sub.3                                                                            F  Cl                         35    CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CONHSO.sub.2 CF.sub.3                                                                 H      F  Cl                         36    CHF.sub.3                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CON(CH.sub.3)SO.sub.2 CF.sub.3                                                        H      F  Cl                         37    CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CONHSO.sub.2 C.sub.2 H.sub.5                                                          H      F  Cl                         38    CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CONHSO.sub.2 C.sub.3 H.sub.7                                                          H      F  Cl                         39    CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CONHSO.sub.2 C.sub.6 H.sub.5                                                          H      F  Cl                         40    CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CONHSO.sub.2 (4-ClC.sub.6 H.sub.4)                                                    H      F  Cl                         41    CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CONHSO.sub.2 (4-CH.sub.3 OC.sub.6                               H.sub.4)              H      F  Cl                         42    CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH.sub.2 CONHSO.sub.2 CH.sub.3                                                                    H      F  Cl                         43    CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH.sub.2 CO.sub.2 H                                                                               H      F  Cl                         44    CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH.sub.2 CO.sub.2 C.sub.2 H.sub.5                                                                 H      F  Cl                         45    CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH.sub.2 CN        H      F  Cl                         46    CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CN     H      F  Cl                         47    CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2 CH(CH.sub.3)CCH                                                              H      F  Cl                         48    CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH.sub.2 COCH.sub.3                                                                               H      F  Cl                         49    CHF.sub.2                                                                              CH.sub.3                                                                             3-OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5                                                              H      F  Cl                         50    CHF.sub.2                                                                              CH.sub.3                                                                             3-OCH(CH.sub.3)CO.sub.2 H                                                                            H      F  Cl                         51    CHF.sub.2                                                                              CH.sub.3                                                                             3-OCH(CH.sub.3)CONH.sub.2                                                                            H      F  Cl                         52    CHF.sub.2                                                                              CH.sub.3                                                                             3-OCH(CH.sub.3)CONHSO.sub.2 CH.sub.3                                                                 H      F  Cl                         53    CHF.sub.2                                                                              CH.sub.3                                                                             3-OCH(CH.sub.3)CONHSO.sub.2 C.sub.6 H.sub.5                                                          H      F  Cl                         54    CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5                                                              2-Cl   F  Cl                         55    CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5                                                              2-F    F  Cl                         56    CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5                                                              3-Cl   F  Cl                         57    CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5                                                              3-F    F  Cl                         58    CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5                                                              2-CH.sub.3                                                                            F  Cl                         59    CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5                                                              3-CH.sub.3                                                                            F  Cl                         60    CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5                                                              2-OCH.sub.3                                                                           F  Cl                         61    CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5                                                              3-OCH.sub.3                                                                           F  Cl                         62    CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5                                                              2-NO.sub.2                                                                            F  Cl                         63    CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5                                                              3-NO.sub.2                                                                            F  Cl                         64    CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5                                                              2,6-F.sub.2                                                                           F  Cl                         65    CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5                                                              2,3-F.sub.2                                                                           F  Cl                         66    CHF.sub.2                                                                              CH.sub.3                                                                             3-OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5                                                              4-NO.sub.2                                                                            F  Cl                         67    CHF.sub.2                                                                              CH.sub.3                                                                             3-OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5                                                              4-Cl   F  Cl                         68    CHF.sub.2                                                                              CH.sub.3                                                                             3-OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5                                                              4-Br   F  Cl                         69    CHF.sub.2                                                                              CH.sub.3                                                                             3-OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5                                                              4-F    F  Cl                         70    CHF.sub.2                                                                              CH.sub.3                                                                             3-OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5                                                              6-F    F  Cl                         71    CHF.sub.2                                                                              CH.sub.3                                                                             3-OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5                                                              4-CN   F  Cl                         72    CHF.sub.2                                                                              CH.sub.3                                                                             3-OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5                                                              4-OCH.sub.3                                                                           F  Cl                         73    CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5                                                              H      H  Br                         74    CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5                                                              H      F  Br                         75    CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5                                                              H      F  CH.sub.3                   76    CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5                                                              H      F  NO.sub.2                   77    CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5                                                              H      F  OCHF.sub.2                 78    CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5                                                              H      F  CF.sub.3                   79    CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5                                                              H      F  F                          80    CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5                                                              H      F  SCH.sub.3                  81    CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5                                                              H      H  Cl                         82    CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5                                                              H      Cl Cl                         83    CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5                                                              H      Br Cl                         84    CHF.sub. 2                                                                             CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5                                                              H      CH.sub.3                                                                          Cl                         85    CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5                                                              H      F  H                          86    CHF.sub.2                                                                              CH.sub.3                                                                             3-OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5                                                              2,4-Cl.sub.2                                                                          H  H                          87    CHF.sub.2                                                                              CH.sub.3                                                                             3-OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5                                                              2F,4Cl H  H                          88    CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2 Na                                                                           H      F  Cl                         89    CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2 K                                                                            H      F  Cl                         90    CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2.sup.- N.sup.+ (C.sub.2                                 H.sub.5).sub.4        H      F  Cl                         91    CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2 CH(CH.sub.3).sub.2                                                           H      F  Cl                         92    CHF.sub.2                                                                              CH.sub.3                                                                             4-NO.sub.2            H      Cl Cl                         93    CHF.sub.2                                                                              CH.sub.3                                                                             4-NH.sub.2            H      Cl Cl                         94    CH.sub.3                                                                               CH.sub.3                                                                             4-NO.sub.2            H      F  Cl                         95    CH.sub.3                                                                               CH.sub.3                                                                             4-NH.sub.2            H      F  Cl                         96    CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2 C(CH.sub.3).sub.2 CCH                                                        H      F  Cl                         97    CHF.sub.2                                                                              CH.sub. 3                                                                            4-CN                  H      F  Cl                         98    CHF.sub.2                                                                              CH.sub.3                                                                             4-NHCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5                                                             H      F  Cl                         99    CH.sub.3                                                                               CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2 CH(CH.sub.3).sub.2                                                           H      F  Cl                         100   CH.sub.3                                                                               CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5                                                              H      F  Cl                         101   CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2 C(CH.sub.3).sub.3                                                            H      F  Cl                         102   CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH.sub.3           H      H  H                          103   CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5                                                              H      H  H                          104   CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH.sub.3           H      F  Cl                         105   CHF.sub.2                                                                              CH.sub.3                                                                             4-OH                  3-Cl   F  Cl                         106   CHF.sub.2                                                                              CH.sub.3                                                                             4-NO.sub.2            2-Cl   F  Cl                         107   CHF.sub.2                                                                              CH.sub.3                                                                             4-NH.sub.2            2-Cl   F  Cl                         108   CHF.sub.2                                                                              CH.sub.3                                                                             4-OH                  2-Cl   F  Cl                         109   CHF.sub.2                                                                              CH.sub.3                                                                             4-NHSO.sub.2 C.sub.2 H.sub.5                                                                         H      F  Cl                         110   CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2 CH.sub.3                                                                     3-Cl   F  Cl                         111   CHF.sub.2                                                                              CH.sub.3                                                                             4-OH                  H      Cl Cl                         112   CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2 CH(CH.sub.3).sub.2                                                           H      Cl Cl                         113   CHF.sub.2                                                                              CH.sub. 3                                                                            4-OCH(CH.sub.3)CO.sub.2 CH.sub.3                                                                     H      Cl Cl                         114   CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2 H                                                                            H      Cl Cl                         115   CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2.sup.- Na.sup.+                                                               H      Cl Cl                         116   CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CONHSO.sub.2 CH.sub.3                                                                 H      Cl Cl                         117   CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2 CH.sub.3                                                                     2-F    F  Cl                         118   CHF.sub.2                                                                              CH.sub.3                                                                             4-NO.sub.2            2-F    F  Cl                         119   CHF.sub.2                                                                              CH.sub.3                                                                             4-NH.sub.2            2-F    F  Cl                         120   CHF.sub.2                                                                              CH.sub.3                                                                             4-OH                  2-F    F  Cl                         121   CHF.sub.2                                                                              CH.sub.3                                                                             4-NH.sub.2            3-OCH.sub.3                                                                           F  Cl                         122   CHF.sub.2                                                                              CH.sub.3                                                                             3-OCH.sub.3           H      F  Cl                         123   CHF.sub.2                                                                              CH.sub.3                                                                             3-OH                  H      F  Cl                         124   CHF.sub.2                                                                              CH.sub.3                                                                             3-OCH(CH.sub.3)CO.sub.2 CH.sub.3                                                                     H      F  Cl                         125   CHF.sub.2                                                                              CH.sub.3                                                                             4-NO.sub.2            3-OCH.sub.3                                                                           F  Cl                         126   CHF.sub.2                                                                              CH.sub.3                                                                             4-CO.sub.2 CH.sub.3   H      F  Cl                         127   CHF.sub.2                                                                              CH.sub.3                                                                             4-CO.sub.2 C.sub.2 H.sub.5                                                                           H      F  Cl                         128   CHF.sub.2                                                                              CH.sub.3                                                                             4-CONHSO.sub.2 (4-ClC.sub.6 H.sub.4)                                                                 H      F  Cl                         129   CHF.sub.2                                                                              CH.sub.3                                                                             4-CONHSO.sub.2 CH.sub.3                                                                              H      F  Cl                         130   CHF.sub.2                                                                              CH.sub.3                                                                             4-CONHSO.sub.2 CH(CH.sub.3).sub.2                                                                    H      F  Cl                         131   CHF.sub.2                                                                              CH.sub.3                                                                             4-OC(CH.sub.3).sub.2 CCH                                                                             H      F  Cl                         132   CHF.sub.2                                                                              CH.sub.3                                                                             4-OH                  H      H  H                          133   CF.sub.2 CHF.sub.2                                                                     CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2 CH.sub.3                                                                     H      F  Cl                         134   CF.sub.2 CHF.sub.2                                                                     CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2 CH.sub.3                                                                     H      Cl Cl                         135   CF.sub.2 CHF.sub.2                                                                     CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5                                                              H      F  Cl                         136   CF.sub.2 CHF.sub.2                                                                     CH.sub.3                                                                             4-OH                  H      F  Cl                         137   CHF.sub.2                                                                              CH.sub.3                                                                             3-OCH(CH.sub.3)CO.sub.2 CH.sub.3                                                                     H      Cl Cl                         138   CHF.sub.2                                                                              CH.sub.3                                                                             3-OCH(CH.sub.3)CO.sub.2 CH.sub.3                                                                     2-F    Cl Cl                         139   CHF.sub.2                                                                              CH.sub.3                                                                             3-OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5                                                              H      Cl Cl                         140   CHF.sub.2                                                                              CH.sub.3                                                                             3-OCH(CH.sub.3)CO.sub.2 C.sub.3 H.sub.7                                                              H      Cl Cl                         141   CHF.sub.2                                                                              CH.sub.3                                                                             3-OCH(CH.sub.3)CO.sub.2 CH(CH.sub.3).sub.2                                                           H      Cl Cl                         142   CHF.sub.2                                                                              CH.sub.3                                                                             3-OCH(CH.sub.3)CO.sub.2 (CH.sub.2).sub.                                        2 O(CH.sub.2).sub.2 OCH.sub.3                                                                        H      Cl Cl                         143   CHF.sub.2                                                                              CH.sub.3                                                                             3-OCH(CH.sub.3)CO.sub.2 (CH.sub.2).sub.2 OCH.sub.3                                                   H      Cl Cl                         144   CHF.sub.2                                                                              CH.sub.3                                                                             3-OCH.sub.3           H      Cl Cl                         145   CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2 CH.sub.3                                                                     2-Cl   F  Cl                         146   CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2 CH(CH.sub.3).sub.2                                                           2-Cl   F  Cl                         147   CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2 C(CH.sub.3).sub.3                                                            2-Cl   F  Cl                         148   CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2 H                                                                            2-Cl   F  Cl                         149   CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5                                                              2-Cl   Cl Cl                         150   CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2 CH.sub.3                                                                     2-Cl   Cl Cl                         151   CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2 C(CH.sub.3).sub.3                                                            2-Cl   Cl Cl                         152   CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH.sub.2 CO.sub.2 CH.sub.3                                                                        2-Cl   Cl Cl                         153   CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2 CH(CH.sub.3).sub.2                                                           2-Cl   Cl Cl                         154   CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2.sup.- Na.sup.+                                                               2-Cl   F  Cl                         155   CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2 C.sub. 2 H.sub.5                                                             2-F    Cl Cl                         156   CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2 CH.sub.3                                                                     2-F    Cl Cl                         157   CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH.sub.2 CO.sub.2 CH.sub.3                                                                        2-F    Cl Cl                         158   CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH.sub.2 CO.sub.2 CH.sub.3                                                                        H      Cl Cl                         159   CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2 (CH.sub.2).sub.2 OCH.sub.3                                                   H      Cl Cl                         160   CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2 CH(CH.sub.3)CH.sub.2 OCH.sub.3                         1                     H      Cl Cl                         161   CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2.sup.- NH.sub.2.sup.+ (C.sub.2                          H.sub.5).sub.2        H      Cl Cl                         162   CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2.sup.- NH.sub.3.sup.+ (CH.sub.2                         ).sub.11 CH.sub.3     H      Cl Cl                         163   CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2 C.sub.3 H.sub.7                                                              H      Cl Cl                         164   CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2 (CH.sub.2).sub.2 O(CH.sub.2).s                         ub.2 OCH.sub.3        H      Cl Cl                         165   CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2 (CH.sub.2).sub.3 CH.sub.3                                                    H      Cl Cl                         166   CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2 (CH.sub.2).sub.                                        2 O(CH.sub.2).sub.2 OCH.sub.3                                                                        2-F    F  Cl                         167   CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CONH.sub.2                                                                            H      Cl Cl                         168   CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2 (CH.sub.2).sub.2 O(CH.sub.2).s                         ub.2 OCH.sub.3        2-F    Cl Cl                         169   CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2 (CH.sub.2).sub.2 OCH.sub.3                                                   H      F  Cl                         170   CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2 (CH.sub.2).sub.2 O(CH.sub.2).s                         ub.2 OCH.sub.3        H      F  Cl                         171   CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH.sub.3           H      H  Cl                         172   CHF.sub.2                                                                              CH.sub.3                                                                              ##STR10##            H      Cl Cl                         173   CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CON(C.sub.2 H.sub.5).sub.2                                                            H      Cl Cl                         174   CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2 (CH.sub.2).sub.17 CH.sub.3                                                   H      Cl Cl                         175   CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2 (CH.sub.2).sub.4 CH.sub.3                                                    H      Cl Cl                         176   CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH.sub.3           H      Cl H                          177   CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2 H                                                                            H      H  H                          178   CHF.sub.2                                                                              CH.sub.3                                                                             3-OH                  H      Cl Cl                         179   CHF.sub.2                                                                              CH.sub.3                                                                             4-NO.sub.2            2-Cl   Cl Cl                         180   CHF.sub.2                                                                              CH.sub.3                                                                             4-NH.sub.2            2-Cl   Cl Cl                         181   CHF.sub.2                                                                              CH.sub.3                                                                             4-OH                  2-Cl   Cl Cl                         182   CHF.sub.2                                                                              CH.sub.3                                                                             5-OCH(CH.sub.3)CO.sub.2 CH.sub.3                                                                     2-Cl   F  Cl                         183   CHF.sub.2                                                                              CH.sub.3                                                                             5-OCH(CH.sub.3)CO.sub.2 H                                                                            2-Cl   F  Cl                         184   CHF.sub.2                                                                              CH.sub.3                                                                             5-OCH(CH.sub.3)CONH.sub.2                                                                            2-Cl   F  Cl                         185   CHF.sub.2                                                                              CH.sub.3                                                                             5-OCH(CH.sub.3)CO.sub.2 CH.sub.3                                                                     2-F    F  Cl                         186   CHF.sub.2                                                                              CH.sub.3                                                                             5-OCH(CH.sub.3)CO.sub.2 H                                                                            2-F    F  Cl                         187   CHF.sub.2                                                                              CH.sub.3                                                                             5-OCH(CH.sub.3)CONH.sub.2                                                                            2-F    F  Cl                         188   CHF.sub.2                                                                              CH.sub.3                                                                             5-OCH(CH.sub.3)CO.sub.2 CH.sub.3                                                                     2-Cl   Cl Cl                         189   CHF.sub.2                                                                              CH.sub.3                                                                             5-OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5                                                              2-Cl   Cl Cl                         190   CHF.sub.2                                                                              CH.sub.3                                                                             5-OCH(CH.sub.3)CO.sub.2 CH(CH.sub.3).sub.2                                                           2-Cl   Cl Cl                         191   CHF.sub.2                                                                              CH.sub.3                                                                             5-OCH(CH.sub.3)CO.sub.2 C.sub.3 H.sub.7                                                              2-Cl   Cl Cl                         192   CHF.sub.2                                                                              CH.sub.3                                                                             5-OCH(CH.sub.3)CO.sub.2 H                                                                            2-Cl   Cl Cl                         193   CHF.sub.2                                                                              CH.sub.3                                                                             5-OCH(CH.sub.3)CONH.sub.2                                                                            2-Cl   Cl Cl                         194   CHF.sub.2                                                                              CH.sub.3                                                                             5-OCH(CH.sub.3)CONHCH.sub.3                                                                          2-Cl   Cl Cl                         195   CHF.sub.2                                                                              CH.sub.3                                                                             5-OCH(CH.sub.3)CON(CH.sub.3).sub.2                                                                   2-Cl   Cl Cl                         196   CHF.sub.2                                                                              CH.sub.3                                                                             5-OCH(CH.sub.3)CONHSO.sub.2 CH.sub.3                                                                 2-Cl   Cl Cl                         197   CHF.sub.2                                                                              CH.sub.3                                                                             5-OCH(CH.sub.3)CO.sub.2 CH.sub.3                                                                     2-F    Cl Cl                         198   CHF.sub.2                                                                              CH.sub.3                                                                             5-OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5                                                              2-F    Cl Cl                         199   CHF.sub.2                                                                              CH.sub.3                                                                             5-OCH(CH.sub.3)CO.sub.2 C.sub.3 H.sub.7                                                              2-F    Cl Cl                         200   CHF.sub.2                                                                              CH.sub.3                                                                             5-OCH.sub.2 CO.sub.2 CH.sub.3                                                                        2-F    Cl Cl                         201   CHF.sub.2                                                                              CH.sub.3                                                                             5-OCH(CH.sub.3)CO.sub.2 H                                                                            2-F    Cl Cl                         202   CHF.sub.2                                                                              CH.sub.3                                                                             5-OCH(CH.sub.3)CN     2-F    Cl Cl                         203   CHF.sub.2                                                                              CH.sub.3                                                                             5-OCH(CH.sub.3)CONH.sub.2                                                                            2-F    Cl Cl                         204   CHF.sub.2                                                                              CH.sub.3                                                                             5-OCH(CH.sub.3)CONHCH.sub.3                                                                          2-F    Cl Cl                         205   CHF.sub.2                                                                              CH.sub.3                                                                             5-OCH(CH.sub.3)CON(CH.sub.3).sub.2                                                                   2-F    Cl Cl                         206   CHF.sub.2                                                                              CH.sub.3                                                                             5-OCH(CH.sub.3)CONHSO.sub.2 CH.sub.3                                                                 2-F    Cl Cl                         207   CHF.sub.2                                                                              CH.sub.3                                                                             5-OCH(CH.sub.3)CONHSO.sub.2 CF.sub.3                                                                 2-F    Cl Cl                         208   CHF.sub.2                                                                              CH.sub.3                                                                             5-OCH.sub.2 CN        2-F    Cl Cl                         209   CHF.sub.2                                                                              CH.sub.3                                                                             5-OCH(CH.sub.3)CO.sub. 2 CH.sub.2 CH.sub.2 OCH.sub.3                                                 2-F    Cl Cl                         210   CHF.sub.2                                                                              CH.sub.3                                                                             5-OCH(CH.sub.3)CO.sub.2 CH(CH.sub.3)CO.sub.2 CH.sub.3                                                2-F    Cl Cl                         211   CHF.sub.2                                                                              CH.sub.3                                                                             5-OCH(CH.sub.3)CO.sub.2 CH.sub.3                                                                     2-Cl,4-NO.sub.2                                                                       F  Cl                         212   CHF.sub.2                                                                              CH.sub.3                                                                             5-OCH(CH.sub.3)CO.sub.2 CH.sub.3                                                                     2-F,4-NO.sub.2                                                                        F  Cl                         213   CHF.sub.2                                                                              CH.sub.3                                                                             5-OCH(CH.sub.3)CO.sub.2 CH.sub.3                                                                     2-Cl,4-NO.sub.2                                                                       Cl Cl                         214   CHF.sub.2                                                                              CH.sub.3                                                                             5-OCH(CH.sub.3)CO.sub.2 CH.sub.3                                                                     2-F,4-NO.sub.2                                                                        Cl Cl                         215   CHF.sub.2                                                                              CH.sub.3                                                                             5-OCH.sub.3           2-F,4-NO.sub.2                                                                        F  Cl                         216   CHF.sub.2                                                                              CH.sub.3                                                                             5-OCH.sub.3           2-F,4-Cl                                                                              F  Cl                         217   CHF.sub.2                                                                              CH.sub.3                                                                             5-OCH.sub.3           2-Cl,4-Cl                                                                             F  Cl                         218   CHF.sub.2                                                                              CH.sub.3                                                                             5-OCH.sub.3           2-Cl,4-NO.sub.2                                                                       Cl Cl                         219   CHF.sub.2                                                                              CH.sub.3                                                                             5-OCH.sub.3           2-F,4-NO.sub.2                                                                        Cl Cl                         220   CHF.sub.2                                                                              CH.sub.3                                                                             5-OCH.sub.3           2,4-Cl.sub.2                                                                          Cl Cl                         221   CHF.sub.2                                                                              CH.sub.3                                                                             3-OCH(CH.sub.3)CO.sub.2 (CH.sub.2).sub.3 O(CH.sub.2).s                         ub.3 OCH.sub.3        H      Cl Cl                         222   CHF.sub.2                                                                              CH.sub.3                                                                             3-OCH(CH.sub.3)CO.sub.2 [CH.sub.2 CH.sub.2 OCH.sub.2                           CH.sub.2 O].sub.2 CH.sub.3                                                                           H      Cl Cl                         223   CHF.sub.2                                                                              CH.sub.3                                                                             3-OCH(CH.sub.3)CO.sub.2 [CH.sub.2 CH.sub.2 OCH.sub.2                           CH.sub.2 O].sub.3 CH.sub.3                                                                           H      Cl Cl                         224   CHF.sub.2                                                                              CH.sub.3                                                                             3-OCH.sub.2 CO.sub.2 CH.sub.2 CH.sub.2 OCH.sub.2                               CH.sub.2 OCH.sub.3    H      Cl Cl                         225   CHF.sub.2                                                                              CH.sub.3                                                                             3-OCH(CH.sub.3 CO.sub.2 (CH.sub.2).sub.3 O(CH.sub.2).s                         ub.3 OCH.sub.3        H      F  Cl                         226   CHF.sub.2                                                                              CH.sub.3                                                                             3-OCH(CH.sub.3)CO.sub.2 [CH.sub.2 CH.sub.2 OCH.sub.2                           CH.sub.2 O].sub.2 CH.sub.3                                                                           H      F  Cl                         227   CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2 (CH.sub.2).sub.3 O(CH.sub.2).s                         ub.3 OCH.sub.3        H      Cl Cl                         228   CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2 [CH.sub.2 CH.sub.2 OCH.sub.2                           CH.sub.2 O].sub.2 CH.sub.3                                                                           H      Cl Cl                         229   CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2 [CH.sub.2 CH.sub.2 OCH.sub.2                           CH.sub.2 O].sub.3 CH.sub.3                                                                           H      Cl Cl                         230   CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH.sub.2 CO.sub.2 CH.sub.2 CH.sub.2 OCH.sub.2                               CH.sub.2 OCH.sub.3    H      Cl Cl                         231   CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub. 2 (CH.sub.2).sub.3 O(CH.sub.2).                         sub.3 OCH.sub.3       H      F  Cl                         232   CHF.sub.2                                                                              CH.sub.3                                                                             4-OCH(CH.sub.3)CO.sub.2 [CH.sub.2 CH.sub.2 OCH.sub.2                           CH.sub.2 O].sub.2 CH.sub.3                                                                           H      F  Cl                         __________________________________________________________________________

Other representative compounds are identical with the foregoing compounds 1-232, respectively, except that in each case the aromatic ring bearing the R² substituent is a pyridine ring of the formula ##STR11## with the R² and R' being in the same positions with respect to the free valence (connected to O) as in said compounds 1-232, see for instance the compounds produced by Examples 3 and 4, and method B above.

                  TABLE 1A                                                         ______________________________________                                         Pyridinyloxyphenyltriazolinones                                                 ##STR12##                                                                     Cmpd No.                                                                               X     Y     R.sup.2         R.sup.a                                                                              R.sup.b                              ______________________________________                                         A1      F     Cl    5-NO.sub.2      CHF.sub.2                                                                            CH.sub.3                             A2      F     Cl    5-NH.sub.2      CHF.sub.2                                                                            CH.sub.3                             A3      F     Cl    5-NHSO.sub.2 (4-ClC.sub.6 H.sub.5)                                                             CHF.sub.2                                                                            CH.sub.3                             A4      F     Cl    5-NHSO.sub.2 C.sub.2 H.sub.5                                                                   CHF.sub.2                                                                            CH.sub.3                             A5      F     Cl    5-OH            CHF.sub.2                                                                            CH.sub.3                             A6      F     Cl    5-OCH(CH.sub.3)CO.sub.2 CH.sub.3                                                               CHF.sub.2                                                                            CH.sub.3                             A7      F     Cl    5-OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5                                                        CHF.sub.2                                                                            CH.sub.3                             A8      F     Cl    5-OCH(CH.sub.3)CO.sub.2 C(CH.sub.3).sub.3                                                      CHF.sub.2                                                                            CH.sub.3                             A9      F     Cl    5-OCH(CH.sub.3)CO.sub.2 CH(CH.sub.3).sub.2                                                     CHF.sub.2                                                                            CH.sub.3                             A10     F     Cl    5-OCH(CH.sub.3)CO.sub.2 H                                                                      CHF.sub.2                                                                            CH.sub.3                             A11     F     Cl    5-OCH.sub.2 CCH CHF.sub.2                                                                            CH.sub.3                             A12     F     Cl    5-OC(O)CH.sub.3 CHF.sub.2                                                                            CH.sub.3                             A13     F     Cl    6-OCH(CH.sub.3)CO.sub.2 CH.sub.3                                                               CHF.sub.2                                                                            CH.sub.3                             A14     F     Cl    6-OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5                                                        CHF.sub.2                                                                            CH.sub.3                             A15     F     Cl    6-OCH(CH.sub.3)CO.sub.2 CH(CH.sub.3).sub.2                                                     CHF.sub.2                                                                            CH.sub.3                             A16     F     Cl    6-OCH(CH.sub.3)CO.sub.2 H                                                                      CHF.sub.2                                                                            CH.sub.3                             A17     F     Cl    6-OCH.sub.2 CO.sub.2 CH.sub.3                                                                  CHF.sub.2                                                                            CH.sub.3                             A18     F     Cl    6-OCH.sub.2 CN  CHF.sub.2                                                                            CH.sub.3                             A19     F     Cl    6-OCH(CH.sub.3)CONH.sub.2                                                                      CHF.sub.2                                                                            CH.sub.3                             A20     F     Cl    6-OCH(CH.sub.3)CONHCH.sub.3                                                                    CHF.sub.2                                                                            CH.sub.3                             A21     F     Cl    6-OCH(CH.sub.3)CON(CH.sub.3).sub.2                                                             CHF.sub.2                                                                            CH.sub.3                             A22     F     Cl    6-OCH(CH.sub.3)CONHSO.sub.2 CH.sub.3                                                           CHF.sub.2                                                                            CH.sub.3                             A23     F     Cl    6-OCH(CH.sub.3)CONHSO.sub.2 CF.sub.3                                                           CHF.sub.2                                                                            CH.sub.3                             A24     Cl    Cl    6-OCH(CH.sub.3)CO.sub.2 CH.sub.3                                                               CHF.sub.2                                                                            CH.sub.3                             A25     Cl    Cl    6-OCH(CH.sub.3)CO.sub.2 H                                                                      CHF.sub.2                                                                            CH.sub.3                             A26     Cl    Cl    6-OCH.sub.2 CO.sub.2 CH.sub.3                                                                  CHF.sub.2                                                                            CH.sub.3                             A27     Cl    Cl    6-OCH.sub.2 CN  CHF.sub.2                                                                            CH.sub.3                             A28     Cl    Cl    6-OCH(CH.sub.3)CONH.sub.2                                                                      CHF.sub.2                                                                            CH.sub.3                             A29     Cl    Cl    6-OCH(CH.sub.3)CONHCH.sub.3                                                                    CHF.sub.2                                                                            CH.sub.3                             A30     Cl    Cl    6-OCH(CH.sub.3)CON(CH.sub.3).sub.2                                                             CHF.sub.2                                                                            CH.sub.3                             ______________________________________                                    

Other representative compounds are identical to the foregoing substituted pyridinyloxy compounds except that the bond from the oxygen to the pyridine ring is at the 3-position or 4-position of the pyridine ring rather than at the 2-position of that ring. In those cases, when the oxygen is at the 3-position, R² is preferably at the 5- or 6-position, and when the oxygen is at the 4-position, R² is preferably at the 2(or 6)-position.

Other representative compounds are identical with the foregoing compounds 1-232, respectively, except that in each case the two benzene rings are connected by sulfur (i.e. Z is sulfur), with the R² and R' being in the same positions with respect to the free valence (connected to S) as in said compounds 1-232.

                                      TABLE 1B                                     __________________________________________________________________________      ##STR13##                                                                     Cmpd                                                                           No. R.sup.a                                                                              R.sup.b                                                                           R.sup.2            R'     X Y                                     __________________________________________________________________________     B1  CF.sub.2 CHF.sub.2                                                                   CH.sub.3                                                                          4-OCH(CH.sub.3)CO.sub.2 CH.sub.3                                                                  H      F Cl                                    B2  CF.sub.2 CHF.sub.2                                                                   CH.sub.3                                                                          4-OCH(CH.sub.3)CO.sub.2 CH.sub.3                                                                  H      Cl                                                                               Cl                                    B3  CF.sub.2 CHF.sub.2                                                                   CH.sub.3                                                                          4-OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5                                                           H      F Cl                                    B4  CF.sub.2 CHF.sub.2                                                                   CH.sub.3                                                                          4-OH               H      F Cl                                    B5  CHF.sub.2                                                                            CH.sub.3                                                                          3-OCH(CH.sub.3)CO.sub.2 CH.sub.3                                                                  H      Cl                                                                               Cl                                    B6  CHF.sub.2                                                                            CH.sub.3                                                                          3-OCH(CH.sub.3)CO.sub.2 CH.sub.3                                                                  2-F    Cl                                                                               Cl                                    B7  CHF.sub.2                                                                            CH.sub.3                                                                          3-OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5                                                           H      Cl                                                                               Cl                                    B8  CHF.sub.2                                                                            CH.sub.3                                                                          3-OCH(CH.sub.3)CO.sub.2 C.sub.3 H.sub.7                                                           H      Cl                                                                               Cl                                    B9  CHF.sub.2                                                                            CH.sub.3                                                                          3-OCH(CH.sub.3)CO.sub.2 CH(CH.sub.3).sub.2                                                        H      Cl                                                                               Cl                                    B10 CHF.sub.2                                                                            CH.sub.3                                                                          3-OCH(CH.sub.3)CO.sub.2 (CH.sub.2).sub.2 O(CH.sub.2)OCH.sub.3                                     H      Cl                                                                               Cl                                    B11 CHF.sub.2                                                                            CH.sub.3                                                                          3-OCH(CH.sub.3)CO.sub.2 (CH.sub.2).sub.2 OCH.sub.3                                                H      Cl                                                                               Cl                                    B12 CHF.sub.2                                                                            CH.sub.3                                                                          3-OCH.sub.3        H      Cl                                                                               Cl                                    B13 CHF.sub.2                                                                            CH.sub.3                                                                          4-OCH(CH.sub.3)CO.sub.2 CH.sub.3                                                                  2-Cl   F Cl                                    B14 CHF.sub.2                                                                            CH.sub.3                                                                          4-OCH(CH.sub.3)CO.sub.2 CH(CH.sub.3).sub.2                                                        2-Cl   F Cl                                    B15 CHF.sub.2                                                                            CH.sub.3                                                                          4-OCH(CH.sub.3)CO.sub.2 C(CH.sub.3).sub.3                                                         2-Cl   F Cl                                    B16 CHF.sub.2                                                                            CH.sub.3                                                                          4-OCH(CH.sub.3)CO.sub.2 H                                                                         2-Cl   F Cl                                    B17 CHF.sub.2                                                                            CH.sub.3                                                                          4-OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5                                                           2-Cl   Cl                                                                               Cl                                    B18 CHF.sub.2                                                                            CH.sub.3                                                                          4-OCH(CH.sub.3)CO.sub.2 CH.sub.3                                                                  2-Cl   Cl                                                                               Cl                                    B19 CHF.sub.2                                                                            CH.sub.3                                                                          4-OCH(CH.sub.3)CO.sub.2 C(CH.sub.3).sub.3                                                         2-Cl   Cl                                                                               Cl                                    B20 CHF.sub.2                                                                            CH.sub.3                                                                          4-OCH.sub.2 CO.sub.2 CH.sub.3                                                                     2-Cl   Cl                                                                               Cl                                    B21 CHF.sub.2                                                                            CH.sub.3                                                                          4-OCH(CH.sub.3)CO.sub.2 CH(CH.sub.3).sub.2                                                        2-Cl   Cl                                                                               Cl                                    B22 CHF.sub.2                                                                            CH.sub.3                                                                          4-OCH(CH.sub.3)CO.sub.2.sup.- Na.sup.+                                                            2-Cl   F Cl                                    B23 CHF.sub.2                                                                            CH.sub.3                                                                          4-OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5                                                           2-F    Cl                                                                               Cl                                    B24 CHF.sub.2                                                                            CH.sub.3                                                                          4-OCH(CH.sub.3)CO.sub.2 CH.sub.3                                                                  2-F    Cl                                                                               Cl                                    B25 CHF.sub.2                                                                            CH.sub.3                                                                          4-OCH.sub.2 CO.sub.2 CH.sub.3                                                                     2-F    Cl                                                                               Cl                                    B26 CHF.sub.2                                                                            CH.sub.3                                                                          4-OCH.sub.2 CO.sub.2 CH.sub.3                                                                     H      Cl                                                                               Cl                                    B27 CHF.sub.2                                                                            CH.sub.3                                                                          4-OCH(CH.sub.3)CO.sub.2 (CH.sub.2).sub.2 OCH.sub.3                                                H      Cl                                                                               Cl                                    B28 CHF.sub.2                                                                            CH.sub.3                                                                          4-OCH(CH.sub.3)CO.sub.2 CH(CH.sub.3)CH.sub.2 OCH.sub.3                                            H      Cl                                                                               Cl                                    B29 CHF.sub.2                                                                            CH.sub.3                                                                          4-OCH(CH.sub.3)CO.sub.2.sup.- NH.sub.2.sup.+ (C.sub.2                          H.sub.5).sub.2     H      Cl                                                                               Cl                                    B30 CHF.sub.2                                                                            CH.sub.3                                                                          4-OCH(CH.sub.3)CO.sub.2.sup.- NH.sub.3.sup.+ (CH.sub.2).sub.1                  1 CH.sub.3         H      Cl                                                                               Cl                                    B31 CHF.sub.2                                                                            CH.sub. 3                                                                         4-OCH(CH.sub.3)CO.sub.2 C.sub.3 H.sub.7                                                           H      Cl                                                                               Cl                                    B32 CHF.sub.2                                                                            CH.sub.3                                                                          4-OCH(CH.sub.3)CO.sub.2 (CH.sub.2).sub.2 O(CH.sub.2).sub.2                     OCH.sub.3          H      Cl                                                                               Cl                                    B33 CHF.sub.2                                                                            CH.sub.3                                                                          4-OCH(CH.sub.3)CO.sub.2 (CH.sub.2).sub.3 CH.sub.3                                                 H      Cl                                                                               Cl                                    B34 CHF.sub.2                                                                            CH.sub.3                                                                          4-OCH(CH.sub.3)CO.sub.2 (CH.sub.2).sub.2 O(CH.sub.2).sub.2                     OCH.sub.3          2-F    F Cl                                    B35 CHF.sub.2                                                                            CH.sub.3                                                                          4-OCH(CH.sub.3)CONH.sub.2                                                                         H      Cl                                                                               Cl                                    B36 CHF.sub.2                                                                            CH.sub.3                                                                          4-OCH(CH.sub.3)CO.sub.2 (CH.sub.2).sub.2 O(CH.sub.2).sub.2                     OCH.sub.3          2-F    Cl                                                                               Cl                                    B37 CHF.sub.2                                                                            CH.sub.3                                                                          4-OCH(CH.sub.3)CO.sub.2 (CH.sub.2).sub.2 OCH.sub.3                                                H      F Cl                                    B38 CHF.sub.2                                                                            CH.sub.3                                                                          4-OCH(CH.sub.3)CO.sub.2 (CH.sub.2).sub.2 O(CH.sub.2).sub.2                     OCH.sub.3          H      F Cl                                    B39 CHF.sub.2                                                                            CH.sub.3                                                                          4-OCH.sub.3        H      H Cl                                    B40 CHF.sub.2                                                                            CH.sub.3                                                                           ##STR14##         H      Cl                                                                               Cl                                    B41 CHF.sub.2                                                                            CH.sub.3                                                                          4-OCH(CH.sub.3)CON(C.sub.2 H.sub.5).sub.2                                                         H      Cl                                                                               Cl                                    B42 CHF.sub.2                                                                            CH.sub.3                                                                          4-OCH(CH.sub.3 )CO.sub.2 (CH.sub.2).sub.17 CH.sub.3                                               H      Cl                                                                               Cl                                    B43 CHF.sub.2                                                                            CH.sub.3                                                                          4-OCH(CH.sub.3)CO.sub.2 (CH.sub.2).sub.4 CH.sub.3                                                 H      Cl                                                                               Cl                                    B44 CHF.sub.2                                                                            CH.sub.3                                                                          4-OCH.sub.3        H      Cl                                                                               H                                     B45 CHF.sub.2                                                                            CH.sub.3                                                                          4-OCH(CH.sub.3)CO.sub.2 H                                                                         H      H H                                     B46 CHF.sub.2                                                                            CH.sub.3                                                                          3-OH               H      Cl                                                                               Cl                                    B47 CHF.sub.2                                                                            CH.sub.3                                                                          4-NO.sub.2         2-Cl   Cl                                                                               Cl                                    B48 CHF.sub.2                                                                            CH.sub.3                                                                          4-NH.sub.2         2-Cl   Cl                                                                               Cl                                    B49 CHF.sub.2                                                                            CH.sub.3                                                                          4-OH               2-Cl   Cl                                                                               Cl                                    B50 CHF.sub.2                                                                            CH.sub.3                                                                          5-OCH(CH.sub.3)CO.sub.2 CH.sub.3                                                                  2-Cl   F Cl                                    B51 CHF.sub.2                                                                            CH.sub.3                                                                          5-OCH(CH.sub.3)CO.sub.2 H                                                                         2-Cl   F Cl                                    B52 CHF.sub.2                                                                            CH.sub.3                                                                          5-OCH(CH.sub.3)CONH.sub.2                                                                         2-Cl   F Cl                                    B53 CHF.sub.2                                                                            CH.sub.3                                                                          5-OCH(CH.sub.3)CO.sub.2 CH.sub.3                                                                  2-F    F Cl                                    B54 CHF.sub.2                                                                            CH.sub.3                                                                          5-OCH(CH.sub.3)CO.sub.2 H                                                                         2-F    F Cl                                    B55 CHF.sub.2                                                                            CH.sub.3                                                                          5-OCH(CH.sub.3)CONH.sub.2                                                                         2-F    F Cl                                    B56 CHF.sub.2                                                                            CH.sub.3                                                                          5-OCH(CH.sub.3)CO.sub.2 CH.sub.3                                                                  2-Cl   Cl                                                                               Cl                                    B57 CHF.sub.2                                                                            CH.sub.3                                                                          5-OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5                                                           2-Cl   Cl                                                                               Cl                                    B58 CHF.sub.2                                                                            CH.sub.3                                                                          5-OCH(CH.sub.3)CO.sub.2 CH(CH.sub.3).sub.2                                                        2-Cl   Cl                                                                               Cl                                    B59 CHF.sub.2                                                                            CH.sub.3                                                                          5-OCH(CH.sub.3)CO.sub.2 C.sub.3 H.sub.7                                                           2-Cl   Cl                                                                               Cl                                    B60 CHF.sub.2                                                                            CH.sub.3                                                                          5-OCH(CH.sub.3)CO.sub.2 H                                                                         2-Cl   Cl                                                                               Cl                                    B61 CHF.sub.2                                                                            CH.sub.3                                                                          5-OCH(CH.sub.3)CONH.sub.2                                                                         2-Cl   Cl                                                                               Cl                                    B62 CHF.sub.2                                                                            CH.sub.3                                                                          5-OCH(CH.sub.3)CONHCH.sub.3                                                                       2-Cl   Cl                                                                               Cl                                    B63 CHF.sub.2                                                                            CH.sub.3                                                                          5-OCH(CH.sub.3)CON(CH.sub.3).sub.2                                                                2-Cl   Cl                                                                               Cl                                    B64 CHF.sub.2                                                                            CH.sub.3                                                                          5-OCH(CH.sub.3)CONHSO.sub.2 CH.sub.3                                                              2-Cl   Cl                                                                               Cl                                    B65 CHF.sub.2                                                                            CH.sub.3                                                                          5-OCH(CH.sub.3)CO.sub.2 CH.sub.3                                                                  2-F    Cl                                                                               Cl                                    B66 CHF.sub.2                                                                            CH.sub.3                                                                          5-OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5                                                           2-F    Cl                                                                               Cl                                    B67 CHF.sub.2                                                                            CH.sub.3                                                                          5-OCH(CH.sub.3)CO.sub.2 C.sub.3 H.sub.7                                                           2-F    Cl                                                                               Cl                                    B68 CHF.sub.2                                                                            CH.sub.3                                                                          5-OCH.sub.2 CO.sub.2 CH.sub.3                                                                     2-F    Cl                                                                               Cl                                    B69 CHF.sub.2                                                                            CH.sub.3                                                                          5-OCH(CH.sub.3)CO.sub.2 H                                                                         2-F    Cl                                                                               Cl                                    B70 CHF.sub.2                                                                            CH.sub.3                                                                          5-OCH(CH.sub.3)CN  2-F    Cl                                                                               Cl                                    B71 CHF.sub.2                                                                            CH.sub.3                                                                          5-OCH(CH.sub.3)CONH.sub.2                                                                         2-F    Cl                                                                               Cl                                    B72 CHF.sub.2                                                                            CH.sub.3                                                                          5-OCH(CH.sub.3)CONHCH.sub.3                                                                       2-F    Cl                                                                               Cl                                    B73 CHF.sub.2                                                                            CH.sub.3                                                                          5-OCH(CH.sub.3)CON(CH.sub.3).sub.2                                                                2-F    Cl                                                                               Cl                                    B74 CHF.sub.2                                                                            CH.sub.3                                                                          5-OCH(CH.sub.3)CONHSO.sub.2 CH.sub.3                                                              2-F    Cl                                                                               Cl                                    B75 CHF.sub.2                                                                            CH.sub.3                                                                          5-OCH(CH.sub.3)CONHSO.sub.2 CF.sub.3                                                              2-F    Cl                                                                               Cl                                    B76 CHF.sub.2                                                                            CH.sub.3                                                                          5-OCH.sub.2 CN     2-F    Cl                                                                               Cl                                    B77 CHF.sub.2                                                                            CH.sub.3                                                                          5-OCH(CH.sub.3)CO.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3                                               2-F    Cl                                                                               Cl                                    B78 CHF.sub.2                                                                            CH.sub.3                                                                          5-OCH(CH.sub.3)CO.sub.2 CH(CH.sub.3)CO.sub.2 CH.sub.3                                             2-F    Cl                                                                               Cl                                    B79 CHF.sub.2                                                                            CH.sub.3                                                                          5-OCH(CH.sub.3)CO.sub.2 CH.sub.3                                                                  2-Cl, 4-NO.sub.2                                                                      F Cl                                    B80 CHF.sub.2                                                                            CH.sub.3                                                                          5-OCH(CH.sub.3)CO.sub.2 CH.sub.3                                                                  2-F, 4-NO.sub.2                                                                       F Cl                                    B81 CHF.sub.2                                                                            CH.sub.3                                                                          5-OCH(CH.sub.3)CO.sub.2 CH.sub.3                                                                  2-Cl, 4-NO.sub.2                                                                      Cl                                                                               Cl                                    B82 CHF.sub.2                                                                            CH.sub.3                                                                          5-OCH(CH.sub.3)CO.sub.2 CH.sub.3                                                                  2-F, 4-NO.sub.2                                                                       Cl                                                                               Cl                                    B83 CHF.sub.2                                                                            CH.sub.3                                                                          5-OCH.sub.3        2-F, 4-NO.sub.2                                                                       F Cl                                    B84 CHF.sub.2                                                                            CH.sub.3                                                                          5-OCH.sub.3        2-F, 4-Cl                                                                             F Cl                                    B85 CHF.sub.2                                                                            CH.sub.3                                                                          5-OCH.sub.3        2-Cl, 4-Cl                                                                            F Cl                                    B86 CHF.sub.2                                                                            CH.sub.3                                                                          5-OCH.sub.3        2-Cl, 4-NO.sub.2                                                                      Cl                                                                               Cl                                    B87 CHF.sub.2                                                                            CH.sub.3                                                                          5-OCH.sub.3        2-F, 4-NO.sub.2                                                                       Cl                                                                               Cl                                    B88 CHF.sub.2                                                                            CH.sub.3                                                                          5-OCH.sub.3        2,4-Cl.sub.2                                                                          Cl                                                                               Cl                                    B89 CHF.sub.2                                                                            CH.sub.3                                                                          4-OCH(CH.sub.3)CO.sub.2 CH.sub.3                                                                  H      Cl                                                                               Cl                                    B90 CHF.sub.2                                                                            CH.sub.3                                                                          4-OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5                                                           H      Cl                                                                               Cl                                    __________________________________________________________________________

Other representative compounds are identical with the foregoing compounds 1-232, respectively, except that in each case the two benzene rings are connected by NR^(c) (i.e. Z is NR^(c)), R^(c) being hydrogen or lower alkyl, with the R² and R' being in the same positions with respect to the free valence (connected to NR^(c)) as in said compounds 1-232.

                                      TABLE 1C                                     __________________________________________________________________________      ##STR15##                                                                     Cmpd                                                                           No. R.sup.a                                                                              R.sup.b                                                                           R.sup.2            R'     X Y                                     __________________________________________________________________________     C1  CF.sub.2 CHF.sub.2                                                                   CH.sub.3                                                                          4-OCH(CH.sub.3)CO.sub.2 CH.sub.3                                                                  H      F Cl                                    C2  CF.sub.2 CHF.sub.2                                                                   CH.sub.3                                                                          4-OCH(CH.sub.3)CO.sub.2 CH.sub.3                                                                  H      Cl                                                                               Cl                                    C3  CF.sub.2 CHF.sub.2                                                                   CH.sub.3                                                                          4-OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5                                                           H      F Cl                                    C4  CF.sub.2 CHF.sub.2                                                                   CH.sub.3                                                                          4-OH               H      F Cl                                    C5  CHF.sub.2                                                                            CH.sub.3                                                                          3-OCH(CH.sub.3)CO.sub.2 CH.sub.3                                                                  H      Cl                                                                               Cl                                    C6  CHF.sub.2                                                                            CH.sub.3                                                                          3-OCH(CH.sub.3)CO.sub.2 CH.sub.3                                                                  2-F    Cl                                                                               Cl                                    C7  CHF.sub.2                                                                            CH.sub.3                                                                          3-OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5                                                           H      Cl                                                                               Cl                                    C8  CHF.sub.2                                                                            CH.sub.3                                                                          3-OCH(CH.sub.3)CO.sub.2 C.sub.3 H.sub.7                                                           H      Cl                                                                               Cl                                    C9  CHF.sub.2                                                                            CH.sub.3                                                                          3-OCH(CH.sub.3)CO.sub.2 CH(CH.sub.3).sub.2                                                        H      Cl                                                                               Cl                                    C10 CHF.sub.2                                                                            CH.sub.3                                                                          3-OCH(CH.sub.3)CO.sub.2 (CH.sub.2).sub.2 O(CH.sub.2).sub.2                     OCH.sub.3          H      Cl                                                                               Cl                                    C11 CHF.sub.2                                                                            CH.sub.3                                                                          3-OCH(CH.sub.3)CO.sub.2 (CH.sub.2).sub.2 OCH.sub.3                                                H      Cl                                                                               Cl                                    C12 CHF.sub.2                                                                            CH.sub.3                                                                          3-OCH.sub.3        H      Cl                                                                               Cl                                    C13 CHF.sub.2                                                                            CH.sub.3                                                                          4-OCH(CH.sub.3)CO.sub.2 CH.sub.3                                                                  2-Cl   F Cl                                    C14 CHF.sub.2                                                                            CH.sub.3                                                                          4-OCH(CH.sub.3)CO.sub.2 CH.sub.2 CH.sub.3                                                         2-Cl   F Cl                                    C15 CHF.sub.2                                                                            CH.sub.3                                                                          4-OCH(CH.sub.3)CO.sub.2 C(CH.sub.3).sub.3                                                         2-Cl   F Cl                                    C16 CHF.sub.2                                                                            CH.sub.3                                                                          4-OCH(CH.sub.3)CO.sub.2 H                                                                         2-Cl   F Cl                                    C17 CHF.sub.2                                                                            CH.sub.3                                                                          4-OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5                                                           2-Cl   Cl                                                                               Cl                                    C18 CHF.sub.2                                                                            CH.sub.3                                                                          4-OCH(CH.sub.3)CO.sub.2 CH.sub.3                                                                  2-Cl   Cl                                                                               Cl                                    C19 CHF.sub.2                                                                            CH.sub.3                                                                          4-OCH(CH.sub.3)CO.sub.2 C(CH.sub.3).sub.3                                                         2-Cl   Cl                                                                               Cl                                    C20 CHF.sub.2                                                                            CH.sub.3                                                                          4-OCH.sub.2 CO.sub.2 CH.sub.3                                                                     2-Cl   Cl                                                                               Cl                                    C21 CHF.sub.2                                                                            CH.sub.3                                                                          4-OCH(CH.sub.3)CO.sub.2 CH(CH.sub.3).sub.2                                                        2-Cl   Cl                                                                               Cl                                    C22 CHF.sub.2                                                                            CH.sub.3                                                                          4-OCH(CH.sub.3)CO.sub.2.sup.- Na.sup.+                                                            2-Cl   F Cl                                    C23 CHF.sub.2                                                                            CH.sub.3                                                                          4-OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5                                                           2-F    Cl                                                                               Cl                                    C24 CHF.sub.2                                                                            CH.sub.3                                                                          4-OCH(CH.sub.3)CO.sub.2 CH.sub.3                                                                  2-F    Cl                                                                               Cl                                    C25 CHF.sub.2                                                                            CH.sub.3                                                                          4-OCH.sub.2 CO.sub.2 CH.sub.3                                                                     2-F    Cl                                                                               Cl                                    C26 CHF.sub.2                                                                            CH.sub.3                                                                          4-OCH.sub.2 CO.sub.2 CH.sub.3                                                                     H      Cl                                                                               Cl                                    C27 CHF.sub.2                                                                            CH.sub.3                                                                          4-OCH(CH.sub.3)CO.sub.2 (CH.sub.2).sub.2 OCH.sub.3                                                H      Cl                                                                               Cl                                    C28 CHF.sub.2                                                                            CH.sub.3                                                                          4-OCH(CH.sub.3)CO.sub.2 CH(CH.sub.3)CH.sub.2 OCH.sub.3                                            H      Cl                                                                               Cl                                    C29 CHF.sub.2                                                                            CH.sub.3                                                                          4-OCH(CH.sub.3)CO.sub.2.sup.- NH.sub.2.sup.+ (C.sub.2                          H.sub.5).sub.2     H      Cl                                                                               Cl                                    C30 CHF.sub.2                                                                            CH.sub.3                                                                          4-OCH(CH.sub.3)CO.sub.2.sup.- NH.sub.3.sup.+ (CH.sub.                          2).sub.11 CH.sub.3 H      Cl                                                                               Cl                                    C31 CHF.sub.2                                                                            CH.sub.3                                                                          4-OCH(CH.sub.3)CO.sub.2 C.sub.3 H.sub.7                                                           H      Cl                                                                               Cl                                    C32 CHF.sub.2                                                                            CH.sub.3                                                                          4-OCH(CH.sub.3)CO.sub.2 (CH.sub.2).sub.2 O(CH.sub.2).sub.2                     OCH.sub.3          H      Cl                                                                               Cl                                    C33 CHF.sub.2                                                                            CH.sub.3                                                                          4-OCH(CH.sub.3)CO.sub.2 (CH.sub.2).sub.3 CH.sub.3                                                 H      Cl                                                                               Cl                                    C34 CHF.sub.2                                                                            CH.sub.3                                                                          4-OCH(CH.sub.3)CO.sub.2 (CH.sub.2).sub.2 O(CH.sub.2).sub.2                     OCH.sub.3          2-F    F Cl                                    C35 CHF.sub.2                                                                            CH.sub.3                                                                          4-OCH(CH.sub.3)CONH.sub.2                                                                         H      Cl                                                                               Cl                                    C36 CHF.sub.2                                                                            CH.sub.3                                                                          4-OCH(CH.sub.3)CO.sub.2 (CH.sub.2).sub.2 O(CH.sub.2).sub.2                     OCH.sub.3          2-F    Cl                                                                               Cl                                    C37 CHF.sub.2                                                                            CH.sub.3                                                                          4-OCH(CH.sub.3)CO.sub.2 (CH.sub.2).sub.2 OCH.sub.3                                                H      F Cl                                    C38 CHF.sub.2                                                                            CH.sub.3                                                                          4-OCH(CH.sub.3)CO.sub.2 (CH.sub.2).sub.2 O(CH.sub.2).sub.2                     OCH.sub.3          H      F Cl                                    C39 CHF.sub.2                                                                            CH.sub.3                                                                          4-OCH.sub.3        H      H Cl                                    C40 CHF.sub.2                                                                            CH.sub.3                                                                           ##STR16##         H      Cl                                                                               Cl                                    C41 CHF.sub.2                                                                            CH.sub.3                                                                          4-OCH(CH.sub.3)CON(C.sub.2 H.sub.5 ).sub.2                                                        H      Cl                                                                               Cl                                    C42 CHF.sub.2                                                                            CH.sub.3                                                                          4-OCH(CH.sub.3)CO.sub.2 (CH.sub.2).sub.17 CH.sub.3                                                H      Cl                                                                               Cl                                    C43 CHF.sub.2                                                                            CH.sub.3                                                                          4-OCH(CH.sub.3)CO.sub.2 (CH.sub.2).sub.4 CH.sub.3                                                 H      Cl                                                                               Cl                                    C44 CHF.sub.2                                                                            CH.sub.3                                                                          4-OCH.sub.3        H      Cl                                                                               H                                     C45 CHF.sub.2                                                                            CH.sub.3                                                                          4-OCH(CH.sub.3)CO.sub.2 H                                                                         H      H H                                     C46 CHF.sub.2                                                                            CH.sub.3                                                                          3-OH               H      Cl                                                                               Cl                                    C47 CHF.sub.2                                                                            CH.sub.3                                                                          4-NO.sub.2         2-Cl   Cl                                                                               Cl                                    C48 CHF.sub.2                                                                            CH.sub.3                                                                          4-NH.sub.2         2-Cl   Cl                                                                               Cl                                    C49 CHF.sub.2                                                                            CH.sub.3                                                                          4-OH               2-Cl   Cl                                                                               Cl                                    C50 CHF.sub.2                                                                            CH.sub.3                                                                          5-OCH(CH.sub.3)CO.sub.2 CH.sub.3                                                                  2-Cl   F Cl                                    C51 CHF.sub.2                                                                            CH.sub.3                                                                          5-OCH(CH.sub.3)CO.sub.2 H                                                                         2-Cl   F Cl                                    C52 CHF.sub.2                                                                            CH.sub.3                                                                          5-OCH(CH.sub.3)CONH.sub.2                                                                         2-Cl   F Cl                                    C53 CHF.sub.2                                                                            CH.sub.3                                                                          5-OCH(CH.sub.3)CO.sub.2 CH.sub.3                                                                  2-F    F Cl                                    C54 CHF.sub.2                                                                            CH.sub.3                                                                          5-OCH(CH.sub.3)CO.sub.2 H                                                                         2-F    F Cl                                    C55 CHF.sub.2                                                                            CH.sub.3                                                                          5-OCH(CH.sub.3)CONH.sub.2                                                                         2-F    F Cl                                    C56 CHF.sub.2                                                                            CH.sub.3                                                                          5-OCH(CH.sub.3)CO.sub.2 CH.sub.3                                                                  2-Cl   Cl                                                                               Cl                                    C57 CHF.sub.2                                                                            CH.sub.3                                                                          5-OCH(CH.sub. 3)CO.sub.2 C.sub.2 H.sub.5                                                          2-Cl   Cl                                                                               Cl                                    C58 CHF.sub.2                                                                            CH.sub.3                                                                          5-OCH(CH.sub.3)CO.sub.2 CH(CH.sub.3).sub.2                                                        2-Cl   Cl                                                                               Cl                                    C59 CHF.sub.2                                                                            CH.sub.3                                                                          5-OCH(CH.sub.3)CO.sub.2 C.sub.3 H.sub.7                                                           2-Cl   Cl                                                                               Cl                                    C60 CHF.sub.2                                                                            CH.sub.3                                                                          5-OCH(CH.sub.3)CO.sub.2 H                                                                         2-Cl   Cl                                                                               Cl                                    C61 CHF.sub.2                                                                            CH.sub.3                                                                          5-OCH(CH.sub.3)CONH.sub.2                                                                         2-Cl   Cl                                                                               Cl                                    C62 CHF.sub.2                                                                            CH.sub.3                                                                          5-OCH(CH.sub.3)CONHCH.sub.3                                                                       2-Cl   Cl                                                                               Cl                                    C63 CHF.sub.2                                                                            CH.sub.3                                                                          5-OCH(CH.sub.3)CON(CH.sub.3).sub.2                                                                2-Cl   Cl                                                                               Cl                                    C64 CHF.sub.2                                                                            CH.sub.3                                                                          5-OCH(CH.sub.3)CONHSO.sub.2 CH.sub.3                                                              2-Cl   Cl                                                                               Cl                                    C65 CHF.sub.2                                                                            CH.sub.3                                                                          5-OCH(CH.sub.3)CO.sub.2 CH.sub.3                                                                  2-F    Cl                                                                               Cl                                    C66 CHF.sub.2                                                                            CH.sub.3                                                                          5-OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5                                                           2-F    Cl                                                                               Cl                                    C67 CHF.sub.2                                                                            CH.sub.3                                                                          5-OCH(CH.sub.3)CO.sub.2 C.sub.3 H.sub.7                                                           2-F    Cl                                                                               Cl                                    C68 CHF.sub.2                                                                            CH.sub.3                                                                          5-OCH.sub.2 CO.sub.2 CH.sub.3                                                                     2-F    Cl                                                                               Cl                                    C69 CHF.sub.2                                                                            CH.sub.3                                                                          5-OCH(CH.sub.3)CO.sub.2 H                                                                         2-F    Cl                                                                               Cl                                    C70 CHF.sub.2                                                                            CH.sub.3                                                                          5-OCH(CH.sub.3)CN  2-F    Cl                                                                               Cl                                    C71 CHF.sub.2                                                                            CH.sub.3                                                                          5-OCH(CH.sub.3)CONH.sub.2                                                                         2-F    Cl                                                                               Cl                                    C72 CHF.sub.2                                                                            CH.sub.3                                                                          5-OCH(CH.sub.3)CONHCH.sub.3                                                                       2-F    Cl                                                                               Cl                                    C73 CHF.sub.2                                                                            CH.sub.3                                                                          5-OCH(CH.sub.3)CON(CH.sub.3).sub.2                                                                2-F    Cl                                                                               Cl                                    C74 CHF.sub.2                                                                            CH.sub.3                                                                          5-OCH(CH.sub.3)CONHSO.sub.2 CH.sub.3                                                              2-F    Cl                                                                               Cl                                    C75 CHF.sub.2                                                                            CH.sub.3                                                                          5-OCH(CH.sub.3)CONHSO.sub.2 CF.sub.3                                                              2-F    Cl                                                                               Cl                                    C76 CHF.sub.2                                                                            CH.sub.3                                                                          5-OCH.sub.2 CN     2-F    Cl                                                                               Cl                                    C77 CHF.sub.2                                                                            CH.sub.3                                                                          5-OCH(CH.sub.3)CO.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3                                               2-F    Cl                                                                               Cl                                    C78 CHF.sub.2                                                                            CH.sub.3                                                                          5-OCH(CH.sub.3)CO.sub.2 CH(CH.sub.3)CO.sub.2 CH.sub.3                                             2-F    Cl                                                                               Cl                                    C79 CHF.sub.2                                                                            CH.sub.3                                                                          5-OCH(CH.sub.3)CO.sub.2 CH.sub.3                                                                  2-Cl, 4-NO.sub.2                                                                      F Cl                                    C80 CHF.sub.2                                                                            CH.sub.3                                                                          5-OCH(CH.sub.3)CO.sub.2 CH.sub.3                                                                  2-F, 4-NO.sub.2                                                                       F Cl                                    C81 CHF.sub.2                                                                            CH.sub.3                                                                          5-OCH(CH.sub.3)CO.sub.2 CH.sub.3                                                                  2-Cl, 4-NO.sub.2                                                                      Cl                                                                               Cl                                    C82 CHF.sub.2                                                                            CH.sub.3                                                                          5-OCH(CH.sub.3)CO.sub.2 CH.sub.3                                                                  2-F, 4-NO.sub.2                                                                       Cl                                                                               Cl                                    C83 CHF.sub.2                                                                            CH.sub.3                                                                          5-OCH.sub.3        2-F, 4-NO.sub.2                                                                       F Cl                                    C84 CHF.sub.2                                                                            CH.sub.3                                                                          5-OCH.sub.3        2-F, 4-Cl                                                                             F Cl                                    C85 CHF.sub.2                                                                            CH.sub.3                                                                          5-OCH.sub.3        2-Cl, 4-Cl                                                                            F Cl                                    C86 CHF.sub.2                                                                            CH.sub.3                                                                          5-OCH.sub.3        2-Cl, 4-NO.sub.2                                                                      Cl                                                                               Cl                                    C87 CHF.sub.2                                                                            CH.sub.3                                                                          5-OCH.sub.3        2-F, 4-NO.sub.2                                                                       Cl                                                                               Cl                                    C88 CHF.sub.2                                                                            CH.sub.3                                                                          5-OCH.sub.3        2,4-Cl.sub.2                                                                          Cl                                                                               Cl                                    C89 CHF.sub.2                                                                            CH.sub.3                                                                          NO.sub.2           H      Cl                                                                               Cl                                    C90 CHF.sub.2                                                                            CH.sub.3                                                                          NH.sub.2           H      Cl                                                                               Cl                                    __________________________________________________________________________

    ______________________________________                                                                        Elemental                                       Cmpd  M.P.      Empirical      Analysis                                        No.   (°C.)                                                                             Formula        C     H    N                                    ______________________________________                                          1      164-165.5                                                                              C.sub.17 H.sub.9 ClF.sub.3 N.sub.5 O.sub.4                                                    C 46.43                                                                              2.06 15.93                                                               F 46.60                                                                              2.28 15.84                                 2    162-165   C.sub.16 H.sub.11 ClF.sub.3 N.sub.3 O.sub.3                     3    133-135   C.sub.16 H.sub.12 ClF.sub.3 N.sub.4 O.sub.2                     4    115-117   C.sub.16 H.sub.10 ClF.sub.3 N.sub.4 O.sub.4                     5    128-129   C.sub.21 H.sub.19 ClF.sub.3 N.sub.3 O.sub.5                                                   C 51.91                                                                              3.94 8.65                                                                F 51.81                                                                              3.69 8.79                                  6    86-88     C.sub.19 H.sub.13 ClF.sub.3 N.sub.3 O.sub.3                                                   C 53.84                                                                              3.09 9.91                                                                F 53.43                                                                              3.07 9.80                                  7    136-138   C.sub.20 H.sub.17 ClF.sub.3 N.sub.3 O.sub.5                                                   C 50.89                                                                              3.64 8.91                                                                F 50.58                                                                              3.53 8.78                                  32   oil       C.sub.20 H.sub. 18 ClF.sub.3 N.sub.4 O.sub.6 S                  91   113.5-115 C.sub.22 H.sub.21 ClF.sub.3 N.sub.3 O.sub.5                     92   thick oil C.sub.16 H.sub.10 Cl.sub.2 F.sub.2 N.sub.4 O.sub.4              27   119-120   C.sub.19 H.sub.16 ClF.sub.3 N.sub.4 O.sub.4                                                   C 49.95                                                                              3.53 12.26                                                               F 49.80                                                                              3.48 12.54                                 29   130-132   C.sub.21 H.sub.20 ClF.sub.3 N.sub.4 O.sub.4                                                   C 52.02                                                                              4.16 11.56                                                               F 51.71                                                                              4.26 11.33                                 43   156.5-158 C.sub.19 H.sub.15 ClF.sub.3 N.sub.3 O.sub.2                                                   C 49.85                                                                              3.30 9.18                                                                F 49.76                                                                              3.60 8.64                                  44   oil       C.sub.20 H.sub.17 ClF.sub.3 N.sub.3 O.sub.5                                                   C 50.91                                                                              3.64 8.91                                                                F 50.62                                                                              3.77 8.84                                  46   oil       C.sub.19 H.sub.14 ClF.sub.3 N.sub.4 O.sub.3                                                   C 52.00                                                                              3.22 12.77                                                               F 51.95                                                                              3.39 12.23                                 49   oil       C.sub.21 H.sub.19 ClF.sub.3 N.sub.3 O.sub.5                     54   oil       C.sub.21 H.sub.18 C1.sub. 2 F.sub.3 N.sub.3 O.sub.5             55   oil       C.sub.21 H.sub.18 ClF.sub.4 N.sub.3 O.sub.5                     56   oil       C.sub.21 H.sub.18 Cl.sub.2 F.sub.3 N.sub.3 O.sub.5              66   111-112   C.sub.21 H.sub.18 ClF.sub.3 N.sub.4 O.sub.7                     82   oil       C.sub.21 H.sub.19 Cl.sub.2 F.sub.2 N.sub.3 O.sub.5                                            C 50.21                                                                              3.82 8.37                                                                F 51.37                                                                              3.95 8.66                                  93   56-59     C.sub.16 H.sub.12 Cl.sub.2 F.sub.2 N.sub.4 O.sub.2              94   117-120   C.sub.16 H.sub.12 ClF.sub. N.sub.4 O.sub.4                      95   155-158   C.sub.16 H.sub.14 ClF.sub. N.sub.4 O.sub.2                      96   oil       C.sub.24 H.sub.21 ClF.sub.3 N.sub.3 O.sub.5                                                   C 55.02                                                                              4.05 8.02                                                                F 55.52                                                                              4.23 7.48                                  97   175-177   C.sub.17 H.sub.10 ClF.sub.3 N.sub.4 O.sub.2                                                   C 51.72                                                                              2.55 14.19                                                               F 51.43                                                                              2.62 13.90                                 98   oil       C.sub.21 H.sub.20 ClF.sub.3 N.sub.4 O.sub.4                                                   C 52.02                                                                              4.17 11.56                                                               F 53.85                                                                              4.19 10.71                                 99   oil       C.sub.22 H.sub.23 ClF.sub. N.sub.3 O.sub.5                                                    C 56.96                                                                              5.00 9.06                                                                F 57.00                                                                              4.74 8.78                                 100   oil       C.sub.21 H.sub.21 ClF.sub. N.sub.3 O.sub.5                                                    C 56.06                                                                              4.20 9.34                                                                F 56.28                                                                              4.47 9.27                                 101     115-117.5                                                                              C.sub.23 H.sub.23 ClF.sub.3 N.sub.3 O.sub.5                                                   C 53.75                                                                              4.51 8.18                                                                F 52.98                                                                              4.31 7.88                                 102   73-75     C.sub.17 H.sub.15 F.sub.2 N.sub.3 O.sub.3                      103   oil       C.sub.21 H.sub.21 F.sub.2 N.sub.3 O.sub.5                                                     C 58.24                                                                              4.88 9.69                                                                F 58.20                                                                              4.91 7.98                                 104   oil       C.sub.17 H.sub.13 ClF.sub.3 N.sub.3 O.sub.3                                                   C 51.07                                                                              3.28 10.51                                                               F 50.31                                                                              3.05 10.32                                105   139-140   C.sub.16 H.sub.10 Cl.sub.2 F.sub.3 N.sub.3 O.sub.3             106   140-141   C.sub.16 H.sub.9 Cl.sub.2 F.sub.3 N.sub.4 O.sub.4              107   112-115   C.sub.16 H.sub.11 Cl.sub.2 F.sub.3 N.sub.4 O.sub.2             108   156- 157  C.sub.16 H.sub.10 Cl.sub.2 F.sub.3 N.sub.3 O.sub.3             109   151-152   C.sub.18 H.sub.16 ClF.sub.3 N.sub.4 O.sub.4 S                                                 C 45.33                                                                              3.38 11.75                                                               F 45.95                                                                              3.80 11.20                                110   oil       C.sub.20 H.sub.16 Cl.sub.2 F.sub.3 N.sub.3 O.sub.5             111   127-128   C.sub.16 H.sub.11 Cl.sub.2 F.sub.2 N.sub.3 O.sub.3             112   121-124   C.sub.22 H.sub.21 Cl.sub.2 F.sub.2 N.sub.3 O.sub.5                                            C 51.17                                                                              4.10 8.14                                                                F 50.34                                                                              4.41 8.49                                 113   120-121   C.sub.20 H.sub.17 Cl.sub.2 F.sub.2 N.sub.3 O.sub.5                                            C 49.19                                                                              3.51 8.61                                                                F 48.81                                                                              3.32 8.53                                 114   185-186   C.sub.19 H.sub.15 Cl.sub.2 F.sub.2 N.sub.3 O.sub.5                                            C 48.12                                                                              3.19 8.86                                                                F 48.40                                                                              3.17 8.62                                 115   160 (dec) C.sub.19 H.sub.14 Cl.sub.2 F.sub.2 N.sub.3 NaO.sub.5           116   150-152   C.sub.20 H.sub.18 Cl.sub.2 F.sub.2 N.sub.4 O.sub.6                                            C 43.57                                                                              3.29 10.15                                                               F 44.48                                                                              3.45 9.07                                 117   oil       C.sub.20 H.sub.16 ClF.sub.4 N.sub.3 O.sub.5                    118   123-125   C.sub.16 H.sub.9 ClF.sub.4 N.sub.4 O.sub.4                     119   149-151   C.sub.16 H.sub.11 ClF.sub.4 N.sub.4 O.sub.2                    120   155-156   C.sub.16 H.sub.10 ClF.sub.4 N.sub.3 O.sub.3                    121   oil       C.sub.17 H.sub.14 ClF.sub.3 N.sub.4 O.sub.3                    122   oil       C.sub.17 H.sub.13 ClF.sub.3 N.sub.3 O.sub.3                    123   oil       C.sub.16 H.sub.11 ClF.sub.3 N.sub.3 O.sub.3                    124   oil       C.sub.20 H.sub.17 ClF.sub.3 N.sub.3 O.sub.5                    125   127-128   C.sub.17 H.sub.12 ClF.sub.3 N.sub.4 O.sub.5                    126   97-98     C.sub.18 H.sub.13 ClF.sub.3 N.sub.3 O.sub.4                                                   C 50.54                                                                              3.06 9.82                                                                F 50.69                                                                              3.01 9.99                                 127   79-81     C.sub.19 H.sub.15 ClF.sub.3 N.sub.3 O.sub.4                                                   C 51.65                                                                              3.43 9.51                                                                F 51.40                                                                              3.58 9.71                                 128    99-100   C.sub.23 H.sub.15 Cl.sub.2 F.sub.3 N.sub.4 O.sub.5                                            C 47.02                                                                              2.58 9.54                                                                F 47.30                                                                              2.72 9.28                                 129   102-104   C.sub.18 H.sub.14 ClF.sub.3 N.sub.4 O.sub.5 S                                                 C 44.04                                                                              2.88 11.41                                                               F 45.04                                                                              2.79 10.86                                130   185-187   C.sub.20 H.sub.18 ClF.sub.3 N.sub.4 O.sub.5 S                                                 C 46.29                                                                              3.50 10.80                                                               F 46.11                                                                              3.41 10.73                                131   oil       C.sub.21 H.sub.17 ClF.sub.3 N.sub.3 O.sub.3                                                   C 55.82                                                                              3.80 9.30                                                                F 55.61                                                                              3.69 9.34                                 132   150-152   C.sub.16 H.sub.13 F.sub.2 N.sub.3 O.sub.3                      137   oil       C.sub.20 H.sub.17 Cl.sub.2 F.sub.2 N.sub.3 O.sub.5             138   oil       C.sub.20 H.sub.16 Cl.sub.2 F.sub.3 N.sub.3 O.sub.5             139   oil       C.sub.21 H.sub.19 Cl.sub.2 F.sub.2 N.sub.3 O.sub.5             140   oil       C.sub.22 H.sub.21 Cl.sub.2 F.sub.2 N.sub.3 O.sub.5             141   oil       C.sub.22 H.sub.21 Cl.sub.2 F.sub.2 N.sub.3 O.sub.5             142   oil       C.sub.24 H.sub.25 Cl.sub.2 F.sub.2 N.sub.3 O.sub.7             143   oil       C.sub.22 H.sub.21 Cl.sub.2 F.sub.2 N.sub.3 O.sub. 6            144   oil       C.sub.17 H.sub.13 Cl.sub.2 F.sub.2 N.sub.3 O.sub.3             145   oil       C.sub.20 H.sub.16 Cl.sub.2 F.sub.3 N.sub.3 O.sub.5             146   oil       C.sub.22 H.sub.20 Cl.sub.2 F.sub.3 N.sub.3 O.sub.5             147   oil       C.sub.23 H.sub.22 Cl.sub.2 F.sub.3 N.sub.3 O.sub.5             148   oil       C.sub.19 H.sub.14 Cl.sub.2 F.sub.3 N.sub.3 O.sub.5             149   oil       C.sub.21 H.sub.18 Cl.sub.3 F.sub.2 N.sub.3 O.sub.5             150   oil       C.sub.20 H.sub.16 Cl.sub.3 F.sub.2 N.sub.3 O.sub.5             151   oil       C.sub.23 H.sub.22 Cl.sub.3 F.sub.2 N.sub.3 O.sub.5             152   oil       C.sub.19 H.sub.14 Cl.sub.3 F.sub.2 N.sub.3 O.sub.5             153   oil       C.sub.22 H.sub.20 Cl.sub.3 F.sub.2 N.sub.3 O.sub.5             154   139-141   C.sub.19 H.sub.13 Cl.sub.2 F.sub.3 N.sub.3 NaO.sub.5           155   oil       C.sub.21 H.sub.18 Cl.sub.2 F.sub.3 N.sub.3 O.sub.5             156   oil       C.sub.20 H.sub.16 Cl.sub.2 F.sub.3 N.sub.3 O.sub.5             157   oil       C.sub.19 H.sub.14 Cl.sub.2 F.sub.3 N.sub.3 O.sub.5             158   126.5-127.5                                                                              C.sub.19 H.sub.15 Cl.sub.2 F.sub.2 N.sub.3 O.sub.5             159   oil       C.sub.22 H.sub.21 Cl.sub.2 F.sub.2 N.sub.3 O.sub.6             160   oil       C.sub.23 H.sub.23 Cl.sub.2 F.sub.2 N.sub.3 O.sub.6             161   oil       C.sub.23 H.sub.26 Cl.sub.2 F.sub.2 N.sub.4 O.sub.5             162   oil       C.sub.31 H.sub.42 Cl.sub.2 F.sub.2 N.sub.4 O.sub.5             163    98-100   C.sub.22 H.sub.21 Cl.sub.2 F.sub.2 N.sub.3 O.sub.5             164   oil       C.sub.24 H.sub.25 Cl.sub.2 F.sub.2 N.sub.3 O.sub.7             165   oil       C.sub.23 H.sub.23 Cl.sub.2 F.sub.2 N.sub.3 O.sub.5             166   oil       C.sub.24 H.sub.24 ClF.sub.4 N.sub.3 O.sub.7                    167   115-117   C.sub.19 H.sub.16 Cl.sub.2 F.sub.2 N.sub.4 O.sub.4             168   oil       C.sub.24 H.sub.24 Cl.sub.2 F.sub.3 N.sub.3 O.sub.7             169   oil       C.sub.22 H.sub.21 ClF.sub.3 N.sub.3 O.sub.6                    170   oil       C.sub.24 H.sub.25 ClF.sub. 3 N.sub.3 O.sub.7                   171   137       C.sub.17 H.sub.14 ClF.sub.2 N.sub.3 O.sub.3                    172   86-88     C.sub.24 H.sub.23 Cl.sub.2 F.sub.2 N.sub.3 O.sub.5             173   113-114   C.sub.23 H.sub.24 Cl.sub.2 F.sub.2 N.sub.4 O.sub.4             174   43-45     C.sub.37 H.sub.51 Cl.sub.2 F.sub.2 N.sub.3 O.sub.5             175   oil       C.sub.24 H.sub.25 Cl.sub.2 F.sub.2 N.sub.3 O.sub.5             176   oil       C.sub.17 H.sub.14 ClF.sub.2 N.sub.3 O.sub.3                    177   90-92     C.sub.19 H.sub.17 F.sub.2 N.sub.3 O.sub.5                      178   68-69     C.sub.16 H.sub.11 Cl.sub.12 F.sub.2 N.sub.3 O.sub.3            179   100-101   C.sub.20 H.sub.17 Cl.sub.2 F.sub.2 N.sub.3 O.sub.4             ______________________________________                                                         S                                                         

                  TABLE 2A                                                         ______________________________________                                                                           Elemental                                    Cmpd  M.P.      Empirical         Analysis                                     No.   (°C.)                                                                             Formula           C    H    N                                  ______________________________________                                         A1    120-123   C.sub.15 H.sub.9 ClF.sub.3 N.sub.5 O.sub.4                                                   C   43.34                                                                               2.18 16.85                                                            F   43.52                                                                               2.35 16.82                              A2    138-140   C.sub.15 H.sub.11 ClF.sub.3 N.sub.5 O.sub.2                    A3    183-185   C.sub.21 H.sub.14 Cl.sub.2 F.sub.3 N.sub.5 O.sub.4                                           C   45.01                                                                               2.52 12.50                                                            F   44.77                                                                               2.58 11.93                              A4    167-168   C.sub.17 H.sub.15 ClF.sub.3 N.sub.5 O.sub.4 S                                                C   42.73                                                                               3.16 14.66                                                            F   42.41                                                                               3.00 14.29                              A5    179-181   C.sub.15 H.sub.10 ClF.sub.3 N.sub.4 O.sub.3                                                  C   46.59                                                                               2.61 14.49                                                            F   46.42                                                                               2.48 14.25                              A6    oil       C.sub.19 H.sub.16 ClF.sub.3 N.sub.4 O.sub.5                                                  C   48.26                                                                               3.41 11.85                                                            F   48.33                                                                               3.54 11.09                              A7    oil       C.sub.20 H.sub.18 ClF.sub.3 N.sub.4 O.sub.5                                                  C   49.34                                                                               3.73 11.51                                                            F   49.16                                                                               3.65 10.82                              A8    oil       C.sub.22 H.sub.22 ClF.sub.3 N.sub.4 O.sub.5                    A9    oil       C.sub.21 H.sub.20 ClF.sub.3 N.sub.4 O.sub.5                                                  C   50.35                                                                               4.03 11.19                                                            F   50.10                                                                               3.75 11.25                               A10  49-51     C.sub.18 H.sub.14 ClF.sub.3 N.sub.4 O.sub.5                     A11  oil       C.sub.18 H.sub.12 ClF.sub.3 N.sub.4 O.sub.3                                                  C   50.90                                                                               2.85 13.19                                                            F   50.07                                                                               2.50 13.05                               A12  120-122   C.sub.17 H.sub.12 ClF.sub.3 N.sub.4 O.sub.4                                                  C   47.62                                                                               2.82 13.07                                                            F   47.16                                                                               3.04 13.04                              ______________________________________                                    

                                      TABLE 3                                      __________________________________________________________________________     Preemergence Herbicidal Activity                                               __________________________________________________________________________             Compound No.                                                                   1   2  3  4   5  6  7  27 29 32  43 44 46 49 54                                Rate (kg/ha)                                                                   8.0 4.0                                                                               4.0                                                                               4.0 4.0                                                                               0.5                                                                               0.5                                                                               0.25                                                                              0.25                                                                              0.125                                                                              0.25                                                                              0.25                                                                              0.125                                                                             0.125                                                                             0.25                      Species % C % C                                                                               % C                                                                               % C % C                                                                               % C                                                                               % C                                                                               % C                                                                               % C                                                                               % C % C                                                                               % C                                                                               % C                                                                               % C                                                                               % C                       __________________________________________________________________________     Cotton  10  70 10  0  70 10 50 100                                                                               10 10  100                                                                               60  0 10 50                        Soybean 10  100                                                                               80 10  70 30 90 50 10 10  90 20 20  0 20                        Corn    50  85 60 20  60 10 95 80 90 10  100                                                                               50  5  0 100                       Rice     0  95 60 20  70 10 80 80 60 40  90 50 70 20 70                        Wheat   20  100                                                                               60 10  80 10 95 95 70 10  95 10  5  0 50                        Morningglory                                                                           20  90 70 10  100                                                                               40 100                                                                               100                                                                               90 80  100                                                                               100                                                                               50 70 100                       Wild Mustard                                                                           --  100                                                                               100                                                                               70  100                                                                               40 100                                                                               100                                                                               100                                                                               70  100                                                                               100                                                                               30 10 100                       Velvetleaf                                                                             80  100                                                                               100                                                                               80  100                                                                               80 100                                                                               100                                                                               100                                                                               100 100                                                                               100                                                                               80 100                                                                               100                       Barnyardgrass                                                                          90  100                                                                               95 30  100                                                                               95 95 100                                                                               100                                                                                0  100                                                                               90 90 20 100                       Green Foxtail                                                                          50  100                                                                               100                                                                               70  100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100 100                                                                               100                                                                               90 10 100                       Johnsongrass                                                                            0  85 100                                                                               70  100                                                                               40 95 100                                                                               95 10  95 70 20 40 100                       __________________________________________________________________________             Compound No.                                                                   55  56 66 82  91 92 93 94 95 96  97 98 99 100                                                                               101                               Rate (kg/ha)                                                                   0.0313                                                                             0.25                                                                               0.25                                                                             0.125                                                                             0.0625                                                                             2.0                                                                               2.0                                                                               2.0                                                                               2.0                                                                               0.125                                                                              2.0                                                                               4.0                                                                               0.25                                                                              0.25                                                                              0.25                      Species % C % C                                                                               % C                                                                               % C                                                                               % C % C                                                                               % C                                                                               % C                                                                               % C                                                                               % C % C                                                                               % C                                                                               % C                                                                               % C                                                                               % C                       __________________________________________________________________________     Cotton  50  100                                                                                0  5  5   0  5  0  0 50   5  0  0  0 80                        Soybean  0  10  5  5  0   0 20  5  0 20  20 40  5  0 20                        Corn     5   0  5  5  5  10  5 10  0  5  40 20  0  0 60                        Rice    40  50 10 20  5   5 10 10  0 50  50  5 20  5 60                        Wheat    0  10  0  0  0  10  5 10 20 50  10  0 10  0 10                        Morningglory                                                                           10  90 20 20 50  10 20  0  0 70  20 10 30 10 95                        Wild Mustard                                                                           80  30  0 10 95   0 10 10 20 80   0 80 60 50 100                       Velvetleaf                                                                             80  90 20 80 100  0  0  0  0 100 40 80 20 10 100                       Barnyardgrass                                                                           0  70  0  0  0  80 50  0  0 20  95 30 20 20 95                        Green Foxtail                                                                           5  90  5 70 80  100                                                                               90 10 10 100 100                                                                               95 60 50 100                       Johnsongrass                                                                           30  70  0 20 40  50 30 50 10 70  70 40 30 30 90                        __________________________________________________________________________             Compound No.                                                                   102 103                                                                               104                                                                               105 106                                                                               107                                                                               108                                                                               109                                                                               110                                                                               111 112                                                                               113                                                                               114                                                                               115                                                                               116                               Rate (kg/ha)                                                                   2.0 2.0                                                                               1.0                                                                               2.0 2.0                                                                               2.0                                                                               2.0                                                                               0.5                                                                               0.25                                                                              2.0 0.25                                                                              0.25                                                                              0.25                                                                              0.25                                                                              0.25                      Species % C % C                                                                               % C                                                                               % C % C                                                                               % C                                                                               % C                                                                               % C                                                                               % C                                                                               % C % C                                                                               % C                                                                               % C                                                                               % C                                                                               % C                       __________________________________________________________________________     Cotton   0   0  5 40   0 40 30 10 20 10  100                                                                               100                                                                               95 100                                                                               100                       Soybean  0   0 20 60  40 100                                                                               70 10 10  0  10  0 10 10  0                        Corn     0   0 70 30  30 20 40  5 40  5  20  5 20 10  0                        Rice     5   0 60 70  50 50 50 30 40 40  70 50 60 40  5                        Wheat    0   0 20 95  80 80 95 40 10 20  40 50 70 10 20                        Morningglory                                                                            0   0 95 80  80 50 100                                                                               10 30 30  80 100                                                                               80 90  5                        Wild Mustard                                                                            0   0 100                                                                               10  10 100                                                                               100                                                                               100                                                                               20  0  100                                                                               100                                                                               95 95  0                        Velvetleaf                                                                              0   0 100                                                                               50  80 100                                                                               100                                                                               90 100                                                                               90  100                                                                               100                                                                               100                                                                               100                                                                               50                        Barnyardgrass                                                                           0   0 100                                                                               100 70 90 100                                                                               60 30 90  80 95 100                                                                               50 10                        Green Foxtail                                                                           0   0 100                                                                               100 95 100                                                                               100                                                                               80 100                                                                               90  100                                                                               100                                                                               100                                                                               100                                                                               20                        Johnsongrass                                                                            0   0 95 50  20 30 95 50 20 70  100                                                                               100                                                                               100                                                                               90 10                        __________________________________________________________________________             Compound No.                                                                   117 118                                                                               119                                                                               120 121                                                                               122                                                                               123                                                                               124 125                                                                               126                                                                               127                                                                               128                                                                               129                                                                               130                                                                               131                               Rate (kg/ha)                                                                   0.0313                                                                             2.0                                                                               2.0                                                                               2.0 2.0                                                                               1.0                                                                               1.0                                                                               0.125                                                                              8.0                                                                               2.0                                                                               2.0                                                                               2.0                                                                               2.0                                                                               2.0                                                                               2.0                       Species % C % C                                                                               % C                                                                               % C % C                                                                               % C                                                                               % C                                                                               % C % C                                                                               % C                                                                               % C                                                                               % C                                                                               % C                                                                               % C                                                                               % C                       __________________________________________________________________________     Cotton  50   0 10 50   0 10  5 30  -- 80 80 90 95 90 50                        Soybean  0   5  5 10  10  0  5  0  20 30 50 40 100                                                                               30 80                        Corn    20  10  5  0   0 20 10  0  20 70 95 20 100                                                                               100                                                                               80                        Rice    10  20 10 10  10 30 20 30  -- 70 80 40 100                                                                               60 80                        Wheat    0   5  0 20   5 10  5 10  100                                                                               10 30 10 95 50 60                        Morningglory                                                                           10  10 60 95  70 80  0 100 70 80 70 90 100                                                                               100                                                                               80                        Wild Mustard                                                                           80   0 60 10   0 40  0 40  -- 95 80 100                                                                               100                                                                               100                                                                               100                       Velvetleaf                                                                             80  20 100                                                                               100 90 95 70 100 95 100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                       Barnyardgrass                                                                          30  50 20 95  50 100                                                                               60 80  90 100                                                                               100                                                                               80 100                                                                               100                                                                               100                       Green Foxtail                                                                          30  80 100                                                                               100 95 100                                                                               30 80  100                                                                               95 100                                                                               80 100                                                                               100                                                                               100                       Johnsongrass                                                                           10  50 40 70  40 90 20 70  -- 80 80 80 100                                                                               100                                                                               100                       __________________________________________________________________________                Compound No.                                                                     132                                                                               145 146 147                                                                               148 149                                                                               150                                                                               151 152                                                                               153                                                                               154                                                                               155                                                                               156                                  Rate (kg/ha)                                                                     8.0                                                                               0.0625                                                                             0.0625                                                                             0.25                                                                              0.0625                                                                             0.125                                                                             0.125                                                                             0.125                                                                              0.125                                                                             0.125                                                                             0.125                                                                             0.25                                                                              0.25                      Species      % C                                                                               % C % C % C                                                                               % C % C                                                                               % C                                                                               % C % C                                                                               % C                                                                               % C                                                                               % C                                                                               % C                       __________________________________________________________________________     Cotton       -- 15  40   0 50   5 30  0  15 10 50 80 70                        Soybean       0 20  15   0 70  50 15  5   5 10 50 90 60                        Corn          0 30  10  10 15  10  5  0   5 15  5 70 60                        Rice         -- 40  30  10 10  40 60  0  80 20 95 95 90                        Wheat         0 30   0   0  5   0 10  0   5  5 15 40 60                        Morningglory  0 70  95  70 70  70 80 70  20 30 100                                                                               100                                                                               100                       Wild Mustard -- 95  100  0 95  95 95  0  70  0 95 100                                                                               100                       Velvetleaf    0 100 100 50 100 90 100                                                                                5  90 50 90 100                                                                               100                       Barnyardgrass                                                                                0 50  60  10 40  20 50  5   5  0 20 70 90                        Green Foxtail                                                                                0 100 100 70 100 100                                                                               100                                                                                0  60 50 90 95 100                       Johnsongrass -- 95  90   5 90  50 70  0  70  0 40 95 100                       __________________________________________________________________________

                                      TABLE 3A                                     __________________________________________________________________________     Preemergence Herbicidal Activity                                                       Compound No.                                                                   A1 A2 A3 A4 A5 A6 A7 A8 A9 A10                                                                               A11                                                                               A12                                           Rate (kg/ha)                                                                   2.0                                                                               2.0                                                                               2.0                                                                               2.0                                                                               2.0                                                                               0.5                                                                               0.5                                                                               0.5                                                                               0.125                                                                             0.5                                                                               2.0                                                                               2.0                                   Species % C                                                                               % C                                                                               % C                                                                               % C                                                                               % C                                                                               % C                                                                               % C                                                                               % C                                                                               % C                                                                               % C                                                                               % C                                                                               % C                                   __________________________________________________________________________     Cotton  30 10 40 50 20 100                                                                               100                                                                               20 20  70                                                                                60                                                                               10                                    Soybean 50 70 10 50 70  70                                                                                40                                                                               20 10  50                                                                                90                                                                               60                                    Corn    30 20  0 90 95 100                                                                               100                                                                               70 20  95                                                                                95                                                                               70                                    Rice    60 60 30 60 90  95                                                                                90                                                                               95 80  95                                                                                90                                                                               50                                    Wheat   90 80 30 70 95  95                                                                                95                                                                               40 30  95                                                                                95                                                                               80                                    Morningglory                                                                           80 80 50 90 95 100                                                                               100                                                                               90 100                                                                               100                                                                               100                                                                               80                                    Wild Mustard                                                                           50 100                                                                               100                                                                               100                                                                               80 100                                                                               100                                                                               95 20 100                                                                               100                                                                               70                                    Velvetleaf                                                                             100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               90 90 100                                                                               100                                                                               100                                   Barnyardgrass                                                                          60 70 40 100                                                                               100                                                                               100                                                                               100                                                                               95 30 100                                                                               100                                                                               100                                   Green Foxtail                                                                          100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               50 100                                                                               100                                                                               100                                   Johnsongrass                                                                           95 70 30 95 80 100                                                                               100                                                                               95 90 100                                                                               100                                                                               80                                    __________________________________________________________________________

                  TABLE 3B                                                         ______________________________________                                         Preemergence Herbicidal Activity                                                                Compound No.                                                                   B89  B90                                                                       Rate (kg/ha)                                                                     0.25   0.125                                                Species            % C    % C                                                  ______________________________________                                         Cotton             --     --                                                   Soybean             0     10                                                   Corn               25     10                                                   Rice               --     --                                                   Wheat               0     0                                                    Morningglory       60     5                                                    Wild Mustard       --     --                                                   Velvetleaf         100    100                                                  Barnyardgrass      --     --                                                   Green Foxtail      80     0                                                    Johnsongrass       30     0                                                    ______________________________________                                    

                  TABLE 3C                                                         ______________________________________                                         Preemergence Herbicidal Activity                                                                Compound No.                                                                   C89* C90*                                                                      Rate (kg/ha)                                                                     0.125  0.125                                                Species            % C    % C                                                  ______________________________________                                         Cotton             --     --                                                   Soybean            0      0                                                    Corn               10     15                                                   Rice               --     --                                                   Wheat              0      0                                                    Morningglory       0      0                                                    Wild Mustard       0      0                                                    Velvetleaf         --     --                                                   Barnyardgrass      --     --                                                   Green Foxtail      0      0                                                    Johnsongrass       0      30                                                   ______________________________________                                          *Z is NH                                                                 

                                      TABLE 4                                      __________________________________________________________________________     Postemergence Herbicidal Activity                                              __________________________________________________________________________             Compound No.                                                                   1  2  3  4  5  6  7  27 29  32 43  44                                          Rate (kg/ha)                                                                   8.0                                                                               4.0                                                                               4.0                                                                               4.0                                                                               4.0                                                                               0.5                                                                               0.5                                                                               0.25                                                                              0.25                                                                               0.125                                                                             0.0625                                                                             0.0625                              Species % C                                                                               % C                                                                               % C                                                                               % C                                                                               % C                                                                               % C                                                                               % C                                                                               % C                                                                               % C % C                                                                               % C % C                                 __________________________________________________________________________     Cotton  60 100                                                                               95 70 100                                                                               95 100                                                                               100                                                                               100 100                                                                                90 100                                 Soybean 60 95 70 50 100                                                                               80 100                                                                               100                                                                                60  70                                                                               100  70                                 Corn    50 95 100                                                                               60 100                                                                               100                                                                               100                                                                               100                                                                               100 100                                                                               100 100                                 Rice    30 95 70 20  95                                                                               60 100                                                                                80                                                                                40  50                                                                                90  10                                 Wheat   20 100                                                                               95 20 100                                                                               95 100                                                                                95                                                                                95  30                                                                               100 100                                 Morningglory                                                                           60 100                                                                               100                                                                               90 100                                                                               100                                                                               100                                                                               100                                                                               100 100                                                                               100 100                                 Wild Mustard                                                                           -- 70 95 70 100                                                                               95 100                                                                               100                                                                               100 100                                                                               100 100                                 Velvetleaf                                                                             100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100 100                                                                               100 100                                 Barnyardgrass                                                                          40 100                                                                               95 30 100                                                                               90 100                                                                               100                                                                               100 100                                                                               100  95                                 Green Foxtail                                                                          80 95 100                                                                               30 100                                                                               95 100                                                                               100                                                                               100 100                                                                                95 100                                 Johnsongrass                                                                           30 95 85 30 100                                                                               95 100                                                                               100                                                                                95 100                                                                               100  80                                 __________________________________________________________________________             Compound No.                                                                   46 49 54 55  56 66 82 91  92 93 94 95                                          Rate (kg/ha)                                                                   0.125                                                                             0.125                                                                             0.25                                                                              0.0313                                                                             0.25                                                                              0.25                                                                              0.125                                                                             0.0625                                                                             2.0                                                                               2.0                                                                               2.0                                                                               2.0                                 Species % C                                                                               % C                                                                               % C                                                                               % C % C                                                                               % C                                                                               % C                                                                               % C % C                                                                               % C                                                                               % C                                                                               % C                                 __________________________________________________________________________     Cotton  80 100                                                                               100                                                                               100 100                                                                               80 100                                                                               100 60 90 30 80                                  Soybean 70  95                                                                                90                                                                               100  80                                                                               60  70                                                                                70 10 50 30 30                                  Corn    70 100                                                                               100                                                                               100 100                                                                               50 100                                                                               100 100                                                                               30 40 30                                  Rice    40  80                                                                                70                                                                                50  50                                                                               10  40                                                                                50 20 20 20 20                                  Wheat   40 100                                                                                95                                                                                95  90                                                                               50  80                                                                                90 20 30 20 10                                  Morningglory                                                                           100                                                                               100                                                                               100                                                                               100 100                                                                               100                                                                               100                                                                               100 40 100                                                                               30 60                                  Wild Mustard                                                                           100                                                                                90                                                                               100                                                                               100 100                                                                               30  50                                                                               100 20 100                                                                               30 10                                  Velvetleaf                                                                             100                                                                               100                                                                               100                                                                               100 100                                                                               100                                                                               100                                                                               100 90 100                                                                               90 60                                  Barnyardgrass                                                                          80 100                                                                               100                                                                                95 100                                                                               50 100                                                                                95 20 30 20 10                                  Green Foxtail                                                                          100                                                                               100                                                                               100                                                                               100 100                                                                               30 100                                                                               100 70 95 30 30                                  Johnsongrass                                                                           100                                                                               100                                                                               100                                                                                95  90                                                                               50 100                                                                                90 30 30 30 30                                  __________________________________________________________________________             Compound No.                                                                   96 97 98 99  100 101 102                                                                               103                                                                               104                                                                               105                                                                               106                                                                               107                                        Rate (kg/ha)                                                                   0.125                                                                             2.0                                                                               4.0                                                                               0.0625                                                                             0.0625                                                                             0.0625                                                                             2.0                                                                               2.0                                                                               1.0                                                                               2.0                                                                               2.0                                                                               2.0                                Species % C                                                                               % C                                                                               % C                                                                               % C % C % C % C                                                                               % C                                                                               % C                                                                               % C                                                                               % C                                                                               % C                                __________________________________________________________________________     Cotton  100                                                                               80 50 80  100 100  5  5 100                                                                               100                                                                               80 95                                 Soybean  90                                                                               60 40 30  40  30   0 10  80                                                                               70 80 95                                 Corn    100                                                                               30 70 30  40  50  10 40 100                                                                               95 80 100                                Rice     70                                                                               20 70  5   0  10  10  5  60                                                                               50 40 50                                 Wheat    50                                                                               30 30 20  20  10   5 10  50                                                                               70 80 95                                 Morningglory                                                                           100                                                                               20 80 50  30  90  10 40 100                                                                               80 100                                                                               100                                Wild Mustard                                                                           100                                                                               30 70 10  10  60  10 20 100                                                                               100                                                                               20 100                                Velvetleaf                                                                             100                                                                               100                                                                               95 90  100 90  10 40 100                                                                               100                                                                               100                                                                               100                                Barnyardgrass                                                                          100                                                                               20 50 30  20  30  10 30 100                                                                               95 70 95                                 Green Foxtail                                                                          100                                                                               70 80 50  10  20  10 20 100                                                                               100                                                                               100                                                                               100                                Johnsongrass                                                                           100                                                                               40 40 30  20  60  10 20  90                                                                               50 50 80                                 __________________________________________________________________________             Compound No.                                                                   108                                                                               109                                                                               110                                                                               111                                                                               112                                                                               113                                                                               114                                                                               115 116                                                                               117 118                                                                               119                                         Rate (kg/ha)                                                                   2.0                                                                               0.5                                                                               0.25                                                                              2.0                                                                               0.25                                                                              0.25                                                                              0.25                                                                              0.25                                                                               0.25                                                                              0.0313                                                                             2.0                                                                               2.0                                 Species % C                                                                               % C                                                                               % C                                                                               % C                                                                               % C                                                                               % C                                                                               % C                                                                               % C % C                                                                               % C % C                                                                               % C                                 __________________________________________________________________________     Cotton  95 95 100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               95  80 100 80 95                                  Soybean 90 50  50                                                                               60  90                                                                                95                                                                                80                                                                               80  40 60  40 40                                  Corn    80 50 100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               90  95 100 50 100                                 Rice    60 50  60                                                                               50  70                                                                                70                                                                                70                                                                               70  40 40  20 50                                  Wheat   95 60  95                                                                               50 100                                                                                90                                                                                95                                                                               95  95 95  30 50                                  Morningglory                                                                           100                                                                               95 100                                                                               70 100                                                                               100                                                                               100                                                                               100 95 100 50 100                                 Wild Mustard                                                                           100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100 90 100  0 80                                  Velvetleaf                                                                             100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100 100                                                                               100 100                                                                               100                                 Barnyardgrass                                                                          100                                                                               60 100                                                                               95 100                                                                               100                                                                               100                                                                               100 90 95  40 90                                  Green Foxtail                                                                          100                                                                               70 100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100 95 95  40 100                                 Johnsongrass                                                                           80 50 100                                                                               95 100                                                                               100                                                                               100                                                                               95  80 90  70 100                                 __________________________________________________________________________             Compound No.                                                                   120                                                                               121                                                                               122                                                                               123                                                                               124                                                                               125                                                                               126                                                                               127                                                                               128                                                                               129                                                                               130                                                                               131                                                                               132                                        Rate (kg/ha)                                                                   2.0                                                                               2.0                                                                               1.0                                                                               1.0                                                                               0.125                                                                             8.0                                                                               2.0                                                                               2.0                                                                               2.0                                                                               2.0                                                                               2.0                                                                               2.0                                                                               8.0                                Species % C                                                                               % C                                                                               % C                                                                               % C                                                                               % C                                                                               % C                                                                               % C                                                                               % C                                                                               % C                                                                               % C                                                                               % C                                                                               % C                                                                               % C                                __________________________________________________________________________     Cotton  100                                                                               100                                                                               90 100                                                                               100                                                                               -- 100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               --                                 Soybean 80 50 50 50  95                                                                               50  90                                                                                60                                                                               90 100                                                                                90                                                                                80                                                                               10                                 Corn    100                                                                               100                                                                               100                                                                               70 100                                                                               60 100                                                                               100                                                                               70 100                                                                               100                                                                               100                                                                               10                                 Rice    95 70 50 70  95                                                                               --  50                                                                                40                                                                               40 100                                                                                90                                                                                50                                                                               --                                 Wheat   40 50 40 40  95                                                                               40  70                                                                                40                                                                               50 100                                                                               100                                                                                95                                                                               10                                 Morningglory                                                                           100                                                                               95 90 50 100                                                                               100                                                                                95                                                                                95                                                                               100                                                                               100                                                                               100                                                                               100                                                                               10                                 Wild Mustard                                                                           40 95 100                                                                               40 100                                                                               -- 100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               --                                 Velvetleaf                                                                             100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               10                                 Barnyardgrass                                                                          95 90 100                                                                               95 100                                                                               20 100                                                                               100                                                                               95 100                                                                               100                                                                                90                                                                               20                                 Green Foxtail                                                                          100                                                                               100                                                                               100                                                                               50 100                                                                               90 100                                                                               100                                                                               95 100                                                                               100                                                                               100                                                                                0                                 Johnsongrass                                                                           95 95 95 50 100                                                                               --  90                                                                                80                                                                               60 100                                                                               100                                                                                90                                                                               --                                 __________________________________________________________________________             Compound No.                                                                   145 146 147                                                                               148 149                                                                               150 151                                                                               152 153 154                                                                               155                                        Rate (kg/ha)                                                                   0.0625                                                                             0.0625                                                                              0.25                                                                             0.0625                                                                             0.125                                                                             0.125                                                                              0.125                                                                             0.125                                                                              0.125                                                                              0.125                                                                             0.25                               Species % C % C % C                                                                               % C % C                                                                               % C % C                                                                               % C % C % C                                                                               % C                                __________________________________________________________________________     Cotton  100 100 60 100 100                                                                               100 70 100 90  100                                                                               100                                Soybean 100 95  60  60 50 90  50  90 40   80                                                                                95                                Field Corn                                                                             100 100 100                                                                               100 100                                                                               100 85 100 100 100                                                                               100                                Rice     70 60  15  60 40 60   5  15 40   20                                                                                85                                Wheat    95 95  30  90 95 85  30  95 30  100                                                                               100                                Morningglory                                                                           100 100 100                                                                               100 100                                                                               100 100                                                                               100 95  100                                                                               100                                Wild Mustard                                                                           100 100 70 100 70 95  30 100  0  100                                                                               100                                Velvetleaf                                                                             100 100 70 100 100                                                                               100 20 100 100 100                                                                               100                                Barnyardgrass                                                                           95 90  15  70 80 95  40  70 10   95                                                                               100                                Green Foxtail                                                                           70 95  80 100 90 100 50 100 50  100                                                                               100                                Johnsongrass                                                                            60 90  30  60 80 95  70  95 50   95                                                                               100                                __________________________________________________________________________                               Compound No.                                                                   156                                                                               157                                                                               158                                                                               159                                                                               160                                                                               161                                                                               162                                                          Rate (kg/ha)                                                                   0.25                                                                              0.25                                                                              0.25                                                                              0.125                                                                             0.125                                                                             0.125                                                                             0.125                                                Species % C                                                                               % C                                                                               % C                                                                               % C                                                                               % C                                                                               % C                                                                               % C                                __________________________________________________________________________                       Cotton  100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                  Soybean  95                                                                                85                                                                                95                                                                                75                                                                               70 75 60                                                   Field Corn                                                                             100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               90                                                   Rice     90                                                                                30                                                                                50                                                                                40                                                                               20 15 10                                                   Wheat   100                                                                                95                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                  Morningglory                                                                           100                                                                               100                                                                               100                                                                               100                                                                               80 60 10                                                   Wild Mustard                                                                            90                                                                               100                                                                               100                                                                                20                                                                               30 30 60                                                   Velvetleaf                                                                             100                                                                               100                                                                               100                                                                               100                                                                               100                                                                                0 90                                                   Barnyardgrass                                                                           70                                                                                95                                                                               100                                                                                80                                                                               90 60 60                                                   Green Foxtail                                                                          100                                                                               100                                                                               100                                                                               -- -- -- --                                                   Johnsongrass                                                                            95                                                                                70                                                                                90                                                                                95                                                                               90 70 70                                 __________________________________________________________________________

                                      TABLE 4A                                     __________________________________________________________________________     Postemergence Herbicidal Activity                                                      Compound No.                                                                   A1 A2 A3 A4 A5 A6 A7 A8 A9 A10                                                                               A11                                                                               A12                                           Rate (kg/ha)                                                                   2.0                                                                               2.0                                                                               2.0                                                                               2.0                                                                               2.0                                                                               0.5                                                                               0.5                                                                               0.5                                                                               0.125                                                                             0.5                                                                               2.0                                                                               2.0                                   Species % C                                                                               % C                                                                               % C                                                                               % C                                                                               % C                                                                               % C                                                                               % C                                                                               % C                                                                               % C                                                                               % C                                                                               % C                                                                               % C                                   __________________________________________________________________________     Cotton  100                                                                               100                                                                               80  50                                                                               100                                                                               100                                                                               100                                                                               100                                                                               95  95                                                                               100                                                                               100                                   Soybean 40 90 80  95                                                                               95 100                                                                                95                                                                                80                                                                               70  70                                                                                95                                                                               95                                    Corn    60 70 40 100                                                                               70 100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               80                                    Rice    10 90 50  95                                                                               70  70                                                                                90                                                                               100                                                                               70 100                                                                                80                                                                               80                                    Wheat   40 90 60 100                                                                               90  95                                                                               100                                                                                95                                                                               100                                                                                90                                                                                80                                                                               70                                    Morningglory                                                                           100                                                                               100                                                                               100                                                                               100                                                                               90 100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                   Wild Mustard                                                                           80 80 100                                                                               100                                                                               90  90                                                                                90                                                                               100                                                                               50  80                                                                               100                                                                               95                                    Velvetleaf                                                                             100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                   Barnyardgrass                                                                          70 90 60  95                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               95                                    Green Foxtail                                                                          100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                                95                                                                               100                                                                               95 100                                                                               100                                                                               95                                    Johnsongrass                                                                           70 80 40  70                                                                               40  95                                                                               100                                                                                95                                                                               90 100                                                                                95                                                                                0                                    __________________________________________________________________________

                  TABLE 4B                                                         ______________________________________                                         Postemergence Herbicidal Activity                                                               Compound No.                                                                   B89  B90                                                                       Rate (kg/ha)                                                                     0.25   0.125                                                Species            % C    % C                                                  ______________________________________                                         Cotton             --     --                                                   Soybean            90     60                                                   Corn               35     15                                                   Rice               --     --                                                   Wheat              80     40                                                   Morningglory       100    100                                                  Wild Mustard       --     --                                                   Velvetleaf         100    100                                                  Barnyardgrass      --     --                                                   Green Foxtail      100    50                                                   Johnsongrass       90     30                                                   ______________________________________                                    

                  TABLE 4C                                                         ______________________________________                                         Postemergence Herbicidal Activity                                                               Compound No.                                                                   C89* C90*                                                                      Rate (kg/ha)                                                                     0.125  0.125                                                Species            % C    % C                                                  ______________________________________                                         Cotton             --     --                                                   Soybean            0      20                                                   Corn               0      35                                                   Rice               --     --                                                   Wheat              0      10                                                   Morningglory       0      50                                                   Wild Mustard       10      0                                                   Velvetleaf         --     --                                                   Barnyardgrass      --     --                                                   Green Foxtail      10     40                                                   Johnsongrass       0      10                                                   ______________________________________                                          *Z is NH                                                                  

I claim:
 1. An herbicidal compound of the formula ##STR17## in which X is halogen, alkyl, haloalkyl or nitro; Y is halogen, alkyl, alkoxy, alkylthio, haloalkyl, nitro, cyano, alkylsulfonylalkyl, --SOCF₃, or halo lower alkoxy;R^(a) is lower haloalkyl, lower alkyl, alkenyl, or alkynyl; R^(b) is hydrogen, halogen, lower alkyl, lower haloalkyl, alkoxy, alkylsulfonyl, alkylthio or haloalkylsulfonyl; R' is H, alkyl, halogen, haloalkyl, nitro, alkoxy, alkylthio or cyano; R² is H, halogen, hydroxy, alkylcarbonyloxy, alkenyloxy, cyano, alkynyloxy, alkyl, haloalkyl, alkoxy, haloalkoxy, nitro, amino, alkylthio, --COOH, --COOR⁷, --CONHSO₂ R⁵, --CONHR⁵, --CONHOR⁷, --COOCH(R⁴)COR³, --NHSO₂ R⁷, --N(SO₂ R⁷)₂, --SCH(R⁴)COR³, --NHCH(R⁴)COR³, R³ [CO --CH--(R⁴)--O--]_(n) -- or NCCH(R⁴)O--[CO--CH(R⁴)--O]_(m) --; provided that where R' is H, halogen, alkyl, or alkoxy, or R^(a) is alkyl; R^(b) is other than H or alkyl, or R² is other than H, halogen, alkyl, or alkoxy; R³ is OH, O⁻ ak⁺, alkoxy, cycloaklyloxy, alkenyloxy, alkynyloxy, --O[CH(R⁸)(CH₂)_(p) O]_(r) R⁹, amino, arylamino, alkylamino, alkenylamino, alkoxyamino, alkylhaloalkyl- or arylsulfonylamino of the formula --NHSO₂ R⁵ or --N(SO₂ R⁵)SO₂ R⁶ ; R⁴ is H or CH₃ ; R⁵ and R⁶ are independently alkyl, haloalkyl or aryl; R⁷ is lower alkyl; R⁸ is H or CH₃ ; R⁹ is alkyl; n is 1 or 2; p is 0 to 5; m is zero or 1; r is 1 to 6; ak⁺ is sodium, potassium, or ammonium; Z is O, S, NH or alkylamino; with the proviso that any cycloalkyl group has from 3 to 7 carbon atoms; any alkyl, alkenyl or alkynyl moiety in Z, R', R₂, R₃, R₅, R₆ or R₉ has 1 to 6 carbon atoms; and any aryl moiety thereof is phenyl, alkoxyphenyl or halophenyl.
 2. A compound as in claim 1 in which R² is [--[OCH(R⁴)^(CO]) n^(R) 3] R³ [CO--CH--(R⁴)--O--]_(n) -- or [--[OCH(R₄)CO]_(m) --OCH(R₄)CN] NCCH(R⁴)O--[CO--CH(R⁴)--O]_(m) --.
 3. A compound as in claim 2 in which n is 1 and m is zero.
 4. A compound as in claim 1 in which R² is [--[OCH(R⁴)CO]N^(R) 3] R³ [CO--CH--(R⁴)--O--]_(n) --.
 5. A compound as in claim 4 in which X and Y are halogen, R^(b) is methyl and R^(a) is difluoromethyl.
 6. A compound as in claim 5 in which X is chlorine, fluorine or bromine and Y is chlorine or bromine at its 4-position.
 7. A compound as in claim 6 in which X is F.
 8. A compound as in claim 7 in which Z is
 0. 9. A compound as in claim 8 in which R⁴ is methyl and n is one.
 10. A compound as in claim 9 in which R² is para to Z.
 11. A compound as in claim 10 in which R³ is lower alkoxy.
 12. A compound as in claim 11 in which R' is F or Cl and is ortho to Z.
 13. A compound as in claim 12 in which R³ is ethoxy and R' is F.
 14. A compound as in claim 13 in which R³ is methoxy and R' is F.
 15. A compound of claim 1 in which R³ is --O[(CH(R⁸)(CH₂)_(p) O]_(r) R⁹.
 16. A compound of claim 15 in which R⁸ is H, p is 1 and r is
 2. 17. An herbicidal composition comprising an herbicidally effective amount of the compound of claim 1 in admixture with a suitable carrier.
 18. A method for controlling undesired plant growth which comprises applying to the locus where control is desired an herbicidally effective amount of the composition of claim
 17. 19. An herbicidal composition comprising an herbicidally effective amount of the compound of claim 4 in admixture with a suitable carrier.
 20. A method for controlling undesired plant growth which comprises applying to the locus where control is desired an herbicidally effective amount of the composition of claim
 19. 21. An herbicidal composition comprising an herbicidally effective amount of the compound of claim 21 in admixture with a suitable carrier.
 22. A method for controlling undesired plant growth which comprises applying to the locus where control is desired an herbicidally effective amount of the composition of claim
 21. 